Nano-linked heteronuclear metallocene catalyst compositions and their polymer products

ABSTRACT

The present invention provides polymerization catalyst compositions employing novel heterodinuclear metallocene compounds. Methods for making these new dinuclear metallocene compounds and for using such compounds in catalyst compositions for the polymerization of olefins are also provided.

BACKGROUND OF THE INVENTION

The present invention relates generally to the field of olefinpolymerization catalysis, catalyst compositions, methods for thepolymerization and copolymerization of olefins, and polyolefins. Morespecifically, this invention relates to nano-linked heterodinuclearmetallocene compounds and catalyst compositions employing suchcompounds.

A dinuclear metallocene compound can be produced via an olefinmetathesis reaction, for example, as shown in Chem. Eur. J., 2003, 9,pp. 3618-3622. Olefin metathesis is a catalytic reaction betweencompounds that contain olefinic (e.g., alkene) moieties. Catalysts thatare often employed in an olefin metathesis reaction include metals suchas ruthenium, tungsten, molybdenum, or nickel.

SUMMARY OF THE INVENTION

The present invention generally relates to new catalyst compositions,methods for preparing catalyst compositions, methods for using thecatalyst compositions to polymerize olefins, the polymer resins producedusing such catalyst compositions, and articles produced using thesepolymer resins. In particular, the present invention relates tonano-linked heterodinuclear metallocene compounds and catalystcompositions employing such compounds. Catalyst compositions containingnano-linked heterodinuclear metallocene compounds of the presentinvention can be used to produce, for example, ethylene-basedhomopolymers, copolymers, terpolymers, and the like.

The present invention discloses novel heterodinuclear metallocenecompounds having two metallocene moieties linked by an alkenyl group.According to one aspect of the present invention, these heterodinuclearcompounds can have one of the following formulas:

wherein:

each X¹, X², X⁵, X⁶, X⁹, and X¹⁰ independently is hydrogen; BH₄; ahalide; a hydrocarbyl group, hydrocarbyloxide group, hydrocarbyloxylategroup, hydrocarbylamino group, or hydrocarbylsilyl group, any of whichhaving up to 20 carbon atoms; or OBR^(A) ₂ or SO₃R^(A), wherein R^(A) isan alkyl group or aryl group having up to 12 carbon atoms;

each X³ independently is a substituted or unsubstitutedcyclopentadienyl, indenyl, or fluorenyl group, any substituents on X³independently are a hydrogen atom or a substituted or unsubstitutedalkyl or alkenyl group;

each X⁴ independently is a substituted cyclopentadienyl, indenyl, orfluorenyl group, any substituents on X⁴ other than an alkenyl linkinggroup independently are a hydrogen atom or a substituted orunsubstituted alkyl or alkenyl group;

each X⁷, X¹¹, and X¹² independently is a substituted cyclopentadienyl,indenyl, or fluorenyl group, any substituents on X⁷, X¹¹, and X¹² otherthan a bridging group independently are a hydrogen atom or a substitutedor unsubstituted alkyl or alkenyl group;

each X⁸ is a substituted cyclopentadienyl, indenyl, or fluorenyl group,any substituents on X⁸ other than a bridging group and an alkenyllinking group independently are a hydrogen atom or a substituted orunsubstituted alkyl or alkenyl group;

each A¹ independently is a substituted or unsubstituted bridging groupcomprising either a cyclic group of 5 to 8 carbon atoms, a bridgingchain of 2 to 5 carbon atoms, or a carbon, silicon, germanium, tin,boron, nitrogen, or phosphorus bridging atom, any substituents on A¹independently are a hydrogen atom, or a substituted or unsubstitutedaliphatic, aromatic, or cyclic group, or a combination thereof;

each A² independently is a substituted bridging group comprising eithera silicon bridging atom, a germanium bridging atom, a tin bridging atom,a carbon bridging atom, or a bridging chain of 2 to 5 carbon atoms, anysubstituents on A² other than the alkenyl linking group independentlyare a hydrogen atom, or a substituted or unsubstituted aliphatic,aromatic, or cyclic group, or a combination thereof;

each M¹, M², and M³ independently is Zr, Hf, or Ti;

each E independently is carbon or silicon;

each R^(X), R^(Y), and R^(Z) independently is a hydrogen atom, or asubstituted or unsubstituted aliphatic, aromatic, or cyclic group, or acombination thereof; and

each n independently is an integer in a range from 0 to 12, inclusive.

Other novel heterodinuclear metallocene compounds are disclosed in thepresent invention, and these dinuclear metallocene compounds can haveone of the following formulas:

(IA)=(IB);

(IIA)=(IIB); or

(IIIA)=(IIIB);

wherein:

wherein:

X¹, X², X⁵, X⁶, X⁹, X¹⁰, X¹³, X¹⁴, X¹⁷, X¹⁸, X²¹, and X²² independentlyare hydrogen; BH₄; a halide; a hydrocarbyl group, hydrocarbyloxidegroup, hydrocarbyloxylate group, hydrocarbylamino group, orhydrocarbylsilyl group, any of which having up to 20 carbon atoms; orOBR^(A) ₂ or SO₃R^(A), wherein R^(A) is an alkyl group or aryl grouphaving up to 12 carbon atoms;

X³ and X¹⁵ independently are a substituted or unsubstitutedcyclopentadienyl, indenyl, or fluorenyl group, any substituents X³ andX¹⁵ independently are a hydrogen atom or a substituted or unsubstitutedalkyl or alkenyl group;

X⁴ and X¹⁶ independently are a substituted cyclopentadienyl, indenyl, orfluorenyl group, any substituents on X⁴ and X¹⁶ other than an alkenyllinking group independently are a hydrogen atom or a substituted orunsubstituted alkyl or alkenyl group;

X⁷, X¹¹, X¹², X¹⁹, X²³, and X²⁴ independently are a substitutedcyclopentadienyl, indenyl, or fluorenyl group, any substituents on X⁷,X¹¹, X¹², X¹⁹, X²³, and X²⁴ other than a bridging group independentlyare a hydrogen atom or a substituted or unsubstituted alkyl or alkenylgroup;

X⁸ and X²⁰ independently are a substituted cyclopentadienyl, indenyl, orfluorenyl group, any substituents on X⁸ and X²⁰ other than a bridginggroup and an alkenyl linking group independently are a hydrogen atom ora substituted or unsubstituted alkyl or alkenyl group;

A¹ and A³ independently are a substituted or unsubstituted bridginggroup comprising either a cyclic group of 5 to 8 carbon atoms, abridging chain of 2 to 5 carbon atoms, or a carbon, silicon, germanium,tin, boron, nitrogen, or phosphorus bridging atom, any substituents onA¹ and A³ independently are a hydrogen atom, or a substituted orunsubstituted aliphatic, aromatic, or cyclic group, or a combinationthereof;

A² and A⁴ independently are a substituted bridging group comprisingeither a silicon bridging atom, a germanium bridging atom, a tinbridging atom, a carbon bridging atom, or a bridging chain of 2 to 5carbon atoms, any substituents on A² and A⁴ other than an alkenyllinking group independently are a hydrogen atom, or a substituted orunsubstituted aliphatic, aromatic, or cyclic group, or a combinationthereof;

M¹, M², M³, M⁴, M⁵, and M⁶ independently are Zr, Hf, or Ti;

each E independently is carbon or silicon;

each R^(X), R^(Y), and R^(Z) independently is a hydrogen atom, or asubstituted or unsubstituted aliphatic, aromatic, or cyclic group, or acombination thereof; and

each n independently is an integer in a range from 0 to 12, inclusive;

with the proviso that (IA) is not the same as (IB), (IIA) is not thesame as (IIB), and (IIIA) is not the same as (IIIB).

In formulas, (IA)=(IB), (IIA)=(IIB), and (IIIA)=(IIIB), the “=” symbolis meant to indicate that the respective metallocene moieties are linkedby a double bond.

Catalyst compositions containing nano-linked heterodinuclear metallocenecompounds are also provided by the present invention. In one aspect, acatalyst composition is disclosed which comprises a contact product of aheterodinuclear metallocene compound and an aluminoxane compound, anorganoboron or organoborate compound, an ionizing ionic compound, or anycombination thereof.

In another aspect, a catalyst composition comprising a contact productof a heterodinuclear metallocene compound and an activator-support isprovided. This catalyst composition can further comprise anorganoaluminum compound, as well as other co-catalysts.

The present invention also contemplates a process for polymerizingolefins in the presence of a catalyst composition, the processcomprising contacting the catalyst composition with an olefin monomerand optionally a comonomer under polymerization conditions to produce anolefin polymer. The catalyst composition, for instance, can comprise acontact product of a heterodinuclear metallocene compound and anactivator-support. Other co-catalysts, including organoaluminumcompounds, can be employed in this process.

Polymers produced from the polymerization of olefins, resulting inhomopolymers, copolymers, and the like, can be used to produce variousarticles of manufacture.

BRIEF DESCRIPTION OF THE FIGURES

FIG. 1 presents a H-NMR plot of catalyst fraction A of Example 1.

FIG. 2 presents a H-NMR plot of catalyst fraction B of Example 1.

FIG. 3 presents a H-NMR plot of catalyst fraction C of Example 1.

FIG. 4 presents a H-NMR plot of catalyst fraction D of Example 1.

FIG. 5 presents a H-NMR plot of a homodinuclear compound based on MET-2.

FIG. 6 presents a H-NMR plot of a homodinuclear compound based on MET-1.

FIG. 7 presents a mass spectrum plot of Example 2.

FIG. 8 presents an expanded mass spectrum plot of Example 2.

FIG. 9 presents a H-NMR plot of Example 17.

FIG. 10 presents a H-NMR plot of a homodinuclear compound based onMET-3.

FIG. 11 presents a mass spectrum plot of Example 18.

DEFINITIONS

To define more clearly the terms used herein, the following definitionsare provided. To the extent that any definition or usage provided by anydocument incorporated herein by reference conflicts with the definitionor usage provided herein, the definition or usage provided hereincontrols.

The term “polymer” is used herein generically to include olefinhomopolymers, copolymers, terpolymers, and so forth. A copolymer isderived from an olefin monomer and one olefin comonomer, while aterpolymer is derived from an olefin monomer and two olefin comonomers.Accordingly, “polymer” encompasses copolymers, terpolymers, etc.,derived from any olefin monomer and comonomer(s) disclosed herein.Similarly, an ethylene polymer would include ethylene homopolymers,ethylene copolymers, ethylene terpolymers, and the like. As an example,an olefin copolymer, such as an ethylene copolymer, can be derived fromethylene and a comonomer, such as 1-butene, 1-hexene, or 1-octene. Ifthe monomer and comonomer were ethylene and 1-hexene, respectively, theresulting polymer would be categorized an as ethylene/1-hexenecopolymer.

In like manner, the scope of the term “polymerization” includeshomopolymerization, copolymerization, terpolymerization, etc. Therefore,a copolymerization process would involve contacting one olefin monomer(e.g., ethylene) and one olefin comonomer (e.g., 1-hexene), to produce acopolymer.

The term “co-catalyst” is used generally herein to refer toorganoaluminum compounds that can constitute one component of a catalystcomposition. Additionally, “co-catalyst” refers to other components of acatalyst composition including, but not limited to, aluminoxanes,organoboron or organoborate compounds, and ionizing ionic compounds, asdisclosed herein. The term “co-catalyst” is used regardless of theactual function of the compound or any chemical mechanism by which thecompound may operate. In one aspect of this invention, the term“co-catalyst” is used to distinguish that component of the catalystcomposition from the dinuclear metallocene compound.

The term “fluoroorgano boron compound” is used herein with its ordinarymeaning to refer to neutral compounds of the form BY₃. The term“fluoroorgano borate compound” also has its usual meaning to refer tothe monoanionic salts of a fluoroorgano boron compound of the form[cation]⁺[BY₄]⁻, where Y represents a fluorinated organic group.Materials of these types are generally and collectively referred to as“organoboron or organoborate compounds.”

The term “contact product” is used herein to describe compositionswherein the components are contacted together in any order, in anymanner, and for any length of time. For example, the components can becontacted by blending or mixing. Further, contacting of any componentcan occur in the presence or absence of any other component of thecompositions described herein. Combining additional materials orcomponents can be done by any suitable method. Further, the term“contact product” includes mixtures, blends, solutions, slurries,reaction products, and the like, or combinations thereof. Although“contact product” can include reaction products, it is not required forthe respective components to react with one another.

The term “precontacted” mixture is used herein to describe a firstmixture of catalyst components that are contacted for a first period oftime prior to the first mixture being used to form a “postcontacted” orsecond mixture of catalyst components that are contacted for a secondperiod of time. Typically, the precontacted mixture describes a mixtureof metallocene compound (or compounds), olefin monomer (or monomers),and organoaluminum compound (or compounds), before this mixture iscontacted with an activator-support(s) and optional additionalorganoaluminum compound. Thus, precontacted describes components thatare used to contact each other, but prior to contacting the componentsin the second, postcontacted mixture. Accordingly, this invention mayoccasionally distinguish between a component used to prepare theprecontacted mixture and that component after the mixture has beenprepared. For example, according to this description, it is possible forthe precontacted organoaluminum compound, once it is contacted with themetallocene and the olefin monomer, to have reacted to form at least onedifferent chemical compound, formulation, or structure from the distinctorganoaluminum compound used to prepare the precontacted mixture. Inthis case, the precontacted organoaluminum compound or component isdescribed as comprising an organoaluminum compound that was used toprepare the precontacted mixture.

Similarly, the term “postcontacted” mixture is used herein to describe asecond mixture of catalyst components that are contacted for a secondperiod of time, and one constituent of which is the “precontacted” orfirst mixture of catalyst components that were contacted for a firstperiod of time. Typically, the term “postcontacted” mixture is usedherein to describe the mixture of metallocene compound(s), olefinmonomer(s), organoaluminum compound(s), and activator-support(s) formedfrom contacting the precontacted mixture of a portion of thesecomponents with any additional components added to make up thepostcontacted mixture. Often, the activator support comprises achemically-treated solid oxide compound. For instance, the additionalcomponent added to make up the postcontacted mixture can be achemically-treated solid oxide compound (or compounds), and optionally,can include an organoaluminum compound which is the same as or differentfrom the organoaluminum compound used to prepare the precontactedmixture, as described herein. Accordingly, this invention may alsooccasionally distinguish between a component used to prepare thepostcontacted mixture and that component after the mixture has beenprepared.

The term “dinuclear metallocene,” as used herein, describes a compoundcomprising two metallocene moieties linked by a connecting group. Theconnecting group can be an alkenyl group resulting from the metathesisreaction or the saturated version resulting from hydrogenation orderivatization. Thus, the dinuclear metallocenes of this inventioncontain four η³ to η⁵-cyclopentadienyl-type moieties, wherein the η³ toη⁵-cycloalkadienyl moieties include cyclopentadienyl ligands, indenylligands, fluorenyl ligands, and the like, including partially saturatedor substituted derivatives or analogs of any of these. Possiblesubstituents on these ligands include hydrogen, therefore thedescription “substituted derivatives thereof” in this inventioncomprises partially saturated ligands such as tetrahydroindenyl,tetrahydrofluorenyl, octahydrofluorenyl, partially saturated indenyl,partially saturated fluorenyl, substituted partially saturated indenyl,substituted partially saturated fluorenyl, and the like. In somecontexts, the dinuclear metallocene is referred to simply as the“catalyst,” in much the same way the term “co-catalyst” is used hereinto refer to, for example, an organoaluminum compound. Unless otherwisespecified, the following abbreviations are used: Cp forcyclopentadienyl; Ind for indenyl; and Flu for fluorenyl.

The terms “catalyst composition,” “catalyst mixture,” “catalyst system,”and the like, do not depend upon the actual product resulting from thecontact or reaction of the components of the mixtures, the nature of theactive catalytic site, or the fate of the co-catalyst, the dinuclearmetallocene compound, any olefin monomer used to prepare a precontactedmixture, or the activator-support, after combining these components.Therefore, the terms “catalyst composition,” “catalyst mixture,”“catalyst system,” and the like, can include both heterogeneouscompositions and homogenous compositions.

The terms “chemically-treated solid oxide,” “solid oxideactivator-support,” “treated solid oxide compound,” and the like, areused herein to indicate a solid, inorganic oxide of relatively highporosity, which exhibits Lewis acidic or Brønsted acidic behavior, andwhich has been treated with an electron-withdrawing component, typicallyan anion, and which is calcined. The electron-withdrawing component istypically an electron-withdrawing anion source compound. Thus, thechemically-treated solid oxide comprises a calcined contact product ofat least one solid oxide with at least one electron-withdrawing anionsource compound. Typically, the chemically-treated solid oxide comprisesat least one ionizing, acidic solid oxide compound. The terms “support”and “activator-support” are not used to imply these components areinert, and such components should not be construed as an inert componentof the catalyst composition. The activator-support of the presentinvention can be a chemically-treated solid oxide.

Although any methods, devices, and materials similar or equivalent tothose described herein can be used in the practice or testing of theinvention, the typical methods, devices and materials are hereindescribed.

All publications and patents mentioned herein are incorporated herein byreference for the purpose of describing and disclosing, for example, theconstructs and methodologies that are described in the publications,which might be used in connection with the presently describedinvention. The publications discussed throughout the text are providedsolely for their disclosure prior to the filing date of the presentapplication. Nothing herein is to be construed as an admission that theinventors are not entitled to antedate such disclosure by virtue ofprior invention.

For any particular compound disclosed herein, any general or specificstructure presented also encompasses all conformational isomers,regioisomers, and stereoisomers that may arise from a particular set ofsubstituents. The general or specific structure also encompasses allenantiomers, diastereomers, and other optical isomers whether inenantiomeric or racemic forms, as well as mixtures of stereoisomers, aswould be recognized by a skilled artisan.

Applicants disclose several types of ranges in the present invention.These include, but are not limited to, a range of number of atoms, arange of integers, a range of weight ratios, a range of molar ratios,and so forth. When Applicants disclose or claim a range of any type,Applicants' intent is to disclose or claim individually each possiblenumber that such a range could reasonably encompass, including endpoints of the range as well as any sub-ranges and combinations ofsub-ranges encompassed therein. For example, when the Applicantsdisclose or claim a chemical moiety having a certain number of carbonatoms, Applicants' intent is to disclose or claim individually everypossible number that such a range could encompass, consistent with thedisclosure herein. For example, the disclosure that a moiety is a C₁ toC₁₀ linear or branched alkyl group, or in alternative language havingfrom 1 to 10 carbon atoms, as used herein, refers to a moiety that canbe selected independently from an alkyl group having 1, 2, 3, 4, 5, 6,7, 8, 9, or 10 carbon atoms, as well as any range between these twonumbers (for example, a C₁ to C₆ alkyl group), and also including anycombination of ranges between these two numbers (for example, a C₂ to C₄and C₆ to C₈ alkyl group).

Similarly, another representative example follows for the weight ratioof organoaluminum to activator-support in a catalyst compositionprovided in one aspect of this invention. By a disclosure that theweight ratio of organoaluminum compound to activator-support is in arange from about 10:1 to about 1:1000, applicants intend to recite thatthe weight ratio can be about 10:1, about 9:1, about 8:1, about 7:1,about 6:1, about 5:1, about 4:1, about 3:1, about 2:1, about 1:1, about1:5, about 1:10, about 1:25, about 1:50, about 1:75, about 1:100, about1:150, about 1:200, about 1:250, about 1:300, about 1:350, about 1:400,about 1:450, about 1:500, about 1:550, about 1:600, about 1:650, about1:700, about 1:750, about 1:800, about 1:850, about 1:900, about 1:950,or about 1:1000. Additionally, the weight ratio can be within any rangefrom about 10:1 to about 1:1000 (for example, the weight ratio is in arange from about 3:1 to about 1:100), and this also includes anycombination of ranges between about 10:1 to about 1:1000. Likewise, allother ranges disclosed herein should be interpreted in a manner similarto these two examples.

Applicants reserve the right to proviso out or exclude any individualmembers of any such group, including any sub-ranges or combinations ofsub-ranges within the group, that can be claimed according to a range orin any similar manner, if for any reason Applicants choose to claim lessthan the full measure of the disclosure, for example, to account for areference that Applicants may be unaware of at the time of the filing ofthe application. Further, Applicants reserve the right to proviso out orexclude any individual substituents, analogs, compounds, ligands,structures, or groups thereof, or any members of a claimed group, if forany reason Applicants choose to claim less than the full measure of thedisclosure, for example, to account for a reference that Applicants maybe unaware of at the time of the filing of the application.

The terms “a,” “an,” and “the” are intended to include pluralalternatives, e.g., at least one, unless otherwise specified. Forinstance, the disclosure of “an activator-support” or “a dinuclearmetallocene compound” is meant to encompass one, or mixtures orcombinations of more than one, activator-support or dinuclearmetallocene compound, respectively.

While compositions and methods are described in terms of “comprising”various components or steps, the compositions and methods can also“consist essentially of” or “consist of” the various components orsteps. For example, a catalyst composition of the present invention cancomprise; alternatively, can consist essentially of; or, alternatively,can consist of; a contact product of (i) a dinuclear metallocenecompound; (ii) an activator-support.

DETAILED DESCRIPTION OF THE INVENTION

The present invention is directed generally to new catalystcompositions, methods for preparing catalyst compositions, methods forusing the catalyst compositions to polymerize olefins, the polymerresins produced using such catalyst compositions, and articles producedusing these polymer resins. In particular, the present invention relatesto nano-linked heterodinuclear metallocene compounds and catalystcompositions employing such compounds.

Nano-linked metallocenes of the present invention are heterodinuclearmolecules in which different metallocene moieties are connected by analkenyl linking group, or nano-link. Nano-linked metallocenes can bedesigned with specific angstrom distances between the two metal centers,where the distance is determined principally by the connecting linkageor linking group. The length, stereochemistry, and flexibility orrigidity of the linking group can be used to design catalysts which areeither capable of, or incapable of, intra-molecular metal-to-metalinteractions. For instance, under the restraint of the nano-link (e.g.,an alkenyl linking group), nano-linked heterodinuclear metallocenes canoffer unique co-catalyst interactions.

Heterodinuclear Metallocene Compounds

The present invention discloses novel compounds having two distinctmetallocene moieties linked by an alkenyl group, and methods of makingthese new compounds. These compounds are commonly referred to asdinuclear compounds, or binuclear compounds, because they contain twometal centers. Accordingly, in one aspect of this invention, theheterodinuclear compounds have the formula:

wherein:

each X¹, X², X⁵, X⁶, X⁹, and X¹⁰ independently is hydrogen; BH₄; ahalide; a hydrocarbyl group, hydrocarbyloxide group, hydrocarbyloxylategroup, hydrocarbylamino group, or hydrocarbylsilyl group, any of whichhaving up to 20 carbon atoms; or OBR^(A) ₂ or SO₃R^(A), wherein R^(A) isan alkyl group or aryl group having up to 12 carbon atoms;

each X³ independently is a substituted or unsubstitutedcyclopentadienyl, indenyl, or fluorenyl group, any substituents on X³independently are a hydrogen atom or a substituted or unsubstitutedalkyl or alkenyl group; each X⁴ independently is a substitutedcyclopentadienyl, indenyl, or fluorenyl group, any substituents on X⁴other than an alkenyl linking group independently are a hydrogen atom ora substituted or unsubstituted alkyl or alkenyl group;

each X⁷, X¹¹, and X¹² independently is a substituted cyclopentadienyl,indenyl, or fluorenyl group, any substituents on X⁷, X¹¹, and X¹² otherthan a bridging group independently are a hydrogen atom or a substitutedor unsubstituted alkyl or alkenyl group;

each X⁸ is a substituted cyclopentadienyl, indenyl, or fluorenyl group,any substituents on X⁸ other than a bridging group and an alkenyllinking group independently are a hydrogen atom or a substituted orunsubstituted alkyl or alkenyl group;

each A¹ independently is a substituted or unsubstituted bridging groupcomprising either a cyclic group of 5 to 8 carbon atoms, a bridgingchain of 2 to 5 carbon atoms, or a carbon, silicon, germanium, tin,boron, nitrogen, or phosphorus bridging atom, any substituents on A¹independently are a hydrogen atom, or a substituted or unsubstitutedaliphatic, aromatic, or cyclic group, or a combination thereof;

each A² independently is a substituted bridging group comprising eithera silicon bridging atom, a germanium bridging atom, a tin bridging atom,a carbon bridging atom, or a bridging chain of 2 to 5 carbon atoms, anysubstituents on A² other than the alkenyl linking group independentlyare a hydrogen atom, or a substituted or unsubstituted aliphatic,aromatic, or cyclic group, or a combination thereof;

each M¹, M², and M³ independently is Zr, Hf, or Ti;

each E independently is carbon or silicon;

each R^(X), R^(Y), and R^(Z) independently is a hydrogen atom, or asubstituted or unsubstituted aliphatic, aromatic, or cyclic group, or acombination thereof; and

each n independently is an integer in a range from 0 to 12, inclusive.

Yet, in another aspect, the heterodinuclear compounds have the formula:

(IA)=(IB);

(IIA)=(IIB); or

(IIIA)=(IIIB);

wherein:

wherein:

X¹, X², X⁵, X⁶, X⁹, X¹⁰, X¹³, X¹⁴, X¹⁷, X¹⁸, X²¹, and X²² independentlyare hydrogen; BH₄; a halide; a hydrocarbyl group, hydrocarbyloxidegroup, hydrocarbyloxylate group, hydrocarbylamino group, orhydrocarbylsilyl group, any of which having up to 20 carbon atoms; orOBR^(A) ₂ or SO₃R^(A), wherein R^(A) is an alkyl group or aryl grouphaving up to 12 carbon atoms;

X³ and X¹⁵ independently are a substituted or unsubstitutedcyclopentadienyl, indenyl, or fluorenyl group, any substituents X³ andX¹⁵ independently are a hydrogen atom or a substituted or unsubstitutedalkyl or alkenyl group;

X⁴ and X¹⁶ independently are a substituted cyclopentadienyl, indenyl, orfluorenyl group, any substituents on X⁴ and X¹⁶ other than an alkenyllinking group independently are a hydrogen atom or a substituted orunsubstituted alkyl or alkenyl group;

X⁷, X¹¹, X¹², X¹⁹, X²³, and X²⁴ independently are a substitutedcyclopentadienyl, indenyl, or fluorenyl group, any substituents on X⁷,X¹¹, X¹², X¹⁹, X²³, and X²⁴ other than a bridging group independentlyare a hydrogen atom or a substituted or unsubstituted alkyl or alkenylgroup;

X⁸ and X²⁰ independently are a substituted cyclopentadienyl, indenyl, orfluorenyl group, any substituents on X⁸ and X²⁰ other than a bridginggroup and an alkenyl linking group independently are a hydrogen atom ora substituted or unsubstituted alkyl or alkenyl group;

A¹ and A³ independently are a substituted or unsubstituted bridginggroup comprising either a cyclic group of 5 to 8 carbon atoms, abridging chain of 2 to 5 carbon atoms, or a carbon, silicon, germanium,tin, boron, nitrogen, or phosphorus bridging atom, any substituents onA¹ and A³ independently are a hydrogen atom, or a substituted orunsubstituted aliphatic, aromatic, or cyclic group, or a combinationthereof;

A² and A⁴ independently are a substituted bridging group comprisingeither a silicon bridging atom, a germanium bridging atom, a tinbridging atom, a carbon bridging atom, or a bridging chain of 2 to 5carbon atoms, any substituents on A² and A⁴ other than an alkenyllinking group independently are a hydrogen atom, or a substituted orunsubstituted aliphatic, aromatic, or cyclic group, or a combinationthereof;

M¹, M², M³, M⁴, M⁵, and M⁶ independently are Zr, Hf, or Ti;

each E independently is carbon or silicon;

each R^(X), R^(Y), and R^(Z) independently is a hydrogen atom, or asubstituted or unsubstituted aliphatic, aromatic, or cyclic group, or acombination thereof; and

each n independently is an integer in a range from 0 to 12, inclusive;

with the proviso that (IA) is not the same as (IB), (IIA) is not thesame as (IIB), and (IIIA) is not the same as (IIIB).

Formulas (A), (B), (C), (IA)=(IB), (IIA)=(IIB), and (IIIA)=(IIIB) above,and any metallocene or dinuclear metallocene species disclosed herein,are not designed to show stereochemistry or isomeric positioning of thedifferent moieties (e.g., these formulas are not intended to display cisor trans isomers, or R or S diastereoisomers), although such compoundsare contemplated and encompassed by these formulas and/or structures. Informulas, (IA)=(IB), (IIA)=(IIB), and (IIIA)=(IIIB), the “=” symbol ismeant to indicate that the respective metallocene moieties are linked bya double bond.

In theses formulas, halides include fluorine, chlorine, bromine, andiodine atoms. As used herein, an aliphatic group includes linear orbranched alkyl and alkenyl groups. Generally, the aliphatic groupcontains from 1 to 20 carbon atoms. Unless otherwise specified, alkyland alkenyl groups described herein are intended to include allstructural isomers, linear or branched, of a given moiety; for example,all enantiomers and all diastereomers are included within thisdefinition. As an example, unless otherwise specified, the term propylis meant to include n-propyl and iso-propyl, while the term butyl ismeant to include n-butyl, iso-butyl, t-butyl, sec-butyl, and so forth.For instance, non-limiting examples of octyl isomers include 2-ethylhexyl and neooctyl. Suitable examples of alkyl groups which can beemployed in the present invention include, but are not limited to,methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, ordecyl, and the like. Examples of alkenyl groups within the scope of thepresent invention include, but are not limited to, ethenyl, propenyl,butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, and thelike.

Aromatic groups and combinations with aliphatic groups include aryl andarylalkyl groups, and these include, but are not limited to, phenyl,alkyl-substituted phenyl, naphthyl, alkyl-substituted naphthyl,phenyl-substituted alkyl, naphthyl-substituted alkyl, and the like.Generally, such groups and combinations of groups contain less thanabout 20 carbon atoms. Hence, non-limiting examples of such moietiesthat can be used in the present invention include phenyl, tolyl, benzyl,dimethylphenyl, trimethylphenyl, phenylethyl, phenylpropyl, phenylbutyl,propyl-2-phenylethyl, and the like. Cyclic groups include cycloalkyl andcycloalkenyl moieties and such moieties can include, but are not limitedto, cyclopentyl, cyclopentenyl, cyclohexyl, cyclohexenyl, and the like.One example of a combination including a cyclic group is acyclohexylphenyl group. Unless otherwise specified, any substitutedaromatic or cyclic moiety used herein is meant to include allregioisomers; for example, the term tolyl is meant to include anypossible substituent position, that is, ortho, meta, or para.

Hydrocarbyl is used herein to specify a hydrocarbon radical group thatincludes, but is not limited to, aryl, alkyl, cycloalkyl, alkenyl,cycloalkenyl, cycloalkadienyl, alkynyl, aralkyl, aralkenyl, aralkynyl,and the like, and includes all substituted, unsubstituted, branched,linear, and/or heteroatom substituted derivatives thereof. Unlessotherwise specified, the hydrocarbyl groups of this invention typicallycomprise up to about 20 carbon atoms. In another aspect, hydrocarbylgroups can have up to 12 carbon atoms, for instance, up to 8 carbonatoms, or up to 6 carbon atoms. A hydrocarbyloxide group, therefore, isused generically to include both alkoxide and aryloxide groups, andthese groups can comprise up to about 20 carbon atoms. Illustrative andnon-limiting examples of alkoxide and aryloxide groups (i.e.,hydrocarbyloxide groups) include methoxy, ethoxy, propoxy, butoxy,phenoxy, substituted phenoxy, and the like. Similarly,hydrocarbyloxylate groups typically have up to about 20 carbon atoms andrepresentative examples include, but are not limited to, formate,acetate, propionate, neopentanoate, 2-ethyl hexanoate, neodecanoate,stearate, oleate, benzoate, and the like. The term hydrocarbylaminogroup is used generically to refer collectively to alkylamino,arylamino, dialkylamino, and diarylamino groups. Unless otherwisespecified, the hydrocarbylamino groups of this invention comprise up toabout 20 carbon atoms. Hydrocarbylsilyl groups include, but are notlimited to, alkylsilyl groups, arylsilyl groups, arylalkylsilyl groups,and the like, which have up to about 20 carbon atoms. For example,hydrocarbylsilyl groups can include trimethylsilyl and phenyloctylsilylgroups. These hydrocarbyloxide, hydrocarbyloxylate, hydrocarbylamino,and hydrocarbylsilyl groups can have up to 12 carbon atoms, oralternatively, up to 8 carbon atoms, in other aspects of the presentinvention.

In the above formulas for heterodinuclear compounds, an alkenyl linkinggroup is an alkenyl group that links or connects the two metallocenemoieties. As illustrated, the alkenyl linking group can be attached tothe respective metallocene moieties at a bridging group or at acyclopentadienyl, indenyl, or fluorenyl group. For example, X⁴ and X¹⁶can have one or more substituents in addition to the alkenyl linkinggroup. Similarly, bridging groups A² and A⁴ can have one or moresubstituents in addition to the alkenyl linking group. Additionally, X⁸and X²⁰ can have one or more substituents in addition to the bridginggroup and the alkenyl linking group.

In one aspect of the present invention, each X¹, X², X⁵, X⁶, X⁹, X¹⁰,X¹³, X¹⁴, X¹⁷, X¹⁸, X²¹, and X²² independently can be hydrogen; BH₄; ahalide; a hydrocarbyl group, hydrocarbyloxide group, hydrocarbyloxylategroup, hydrocarbylamino group, or hydrocarbylsilyl group, any of whichhaving up to 20 carbon atoms; or OBR^(A) ₂ or SO₃R^(A), wherein R^(A) isan alkyl group or aryl group having up to 12 carbon atoms. In anotheraspect, each X¹, X², X⁵, X⁶, X⁹, X¹⁰, X¹³, X¹⁴, X¹⁷, X¹⁸, X²¹, and X²²independently is methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl,octyl, nonyl, decyl, or trimethylsilylmethyl. In yet another aspect,each X¹, X², X⁵, X⁶, X⁹, X¹⁰, X¹³, X¹⁴, X¹⁷, X¹⁸, X²¹, and X²²independently is ethenyl, propenyl, butenyl, pentenyl, hexenyl,heptenyl, octenyl, nonenyl, or decenyl. Each X¹, X², X⁵, X⁶, X⁹, X¹⁰,X¹³, X¹⁴, X¹⁷, X¹⁸, X²¹, and X²² independently is a substituted orunsubstituted aromatic group, for example, having up to 20 carbon atoms,in another aspect of the present invention.

In a different aspect, each X¹, X², X⁵, X⁶, X⁹, X¹⁰, X¹³, X¹⁴, X¹⁷, X¹⁸,X²¹, and X²² is a chlorine atom. Each X¹, X², X⁵, X⁶, X⁹, X¹⁰, X¹³, X¹⁴,X¹⁷, X¹⁸, X²¹, and X²² independently can be phenyl, naphthyl, tolyl,benzyl, dimethylphenyl, trimethylphenyl, phenylethyl, phenylpropyl,phenylbutyl, propyl-2-phenylethyl, cyclopentyl, cyclopentenyl,cyclohexyl, cyclohexenyl, or cyclohexylphenyl in other aspects of thisinvention. Yet, in another aspect, each X¹, X², X⁵, X⁶, X⁹, X¹⁰, X¹³,X¹⁴, X¹⁷, X¹⁸, X²¹, and X²² independently is methyl, phenyl, benzyl, ora halide. Further, each X¹, X², X⁵, X⁶, X⁹, X¹⁰, X¹³, X¹⁴, X¹⁷, X¹⁸,X²¹, and X²² independently can be methyl, phenyl, benzyl, or a chlorineatom in another aspect of the present invention.

In the above formulas, each X³ and X¹⁵ independently is a substituted orunsubstituted cyclopentadienyl, indenyl, or fluorenyl group, while eachX⁴ and X¹⁶ independently is a substituted cyclopentadienyl, indenyl, orfluorenyl group. In some aspects of this invention, each X³ and X¹⁵independently is a substituted or unsubstituted cyclopentadienyl group.In other aspects, each X⁴ and X¹⁶ independently is a substitutedcyclopentadienyl or substituted indenyl group.

Each X⁷, X¹¹, X¹², X¹⁹, X²³, and X²⁴ independently is a substitutedcyclopentadienyl, indenyl, or fluorenyl group, and are necessarilysubstituted with a bridging group, as indicated in the formulas above.For instance, each X⁷ and X¹⁹ can be a substituted fluorenyl group,while in certain aspects of this invention, at least one of X¹¹ and X¹²and at least one of X²³ and X²⁴ is a substituted fluorenyl group.

Similarly, each X⁸ and X²⁰ independently is a substitutedcyclopentadienyl, indenyl, or fluorenyl group, and are necessarilysubstituted with a bridging group and an alkenyl linking group, asindicated in the formulas above. In accordance with an aspect of thepresent invention, each X⁸ and X²⁰ is a substituted cyclopentadienylgroup.

Each A¹ and A³ independently can be a substituted or unsubstitutedbridging group comprising either a cyclic group of 5 to 8 carbon atoms,a bridging chain of 2 to 5 carbon atoms, or a carbon, silicon,germanium, tin, boron, nitrogen, or phosphorus bridging atom. Each A²and A⁴ independently can be a substituted bridging group comprisingeither a silicon bridging atom, a germanium bridging atom, a tinbridging atom, a carbon bridging atom, or a bridging chain of 2 to 5carbon atoms. In one aspect of this invention, each A¹, A², A³, and A⁴independently is a carbon, silicon, germanium, or tin bridging atom; oralternatively, a carbon bridging atom. Yet, in another aspect, each A¹,A², A³, and A⁴ independently is a bridging chain of 2 to 5 carbon atoms,such as, for example, a two-carbon bridging chain that connects therespective cyclopentadienyl-type moieties.

Any substituents on X³, X⁴, X⁷, X⁸, X¹¹, X¹², X¹⁵, X¹⁶, X¹⁹, X²⁰, X²³,and X²⁴ (other than a bridging group and/or an alkenyl linking group, asthe context requires) independently are a hydrogen atom or a substitutedor unsubstituted alkyl or alkenyl group. Hydrogen is included, thereforethe notion of a substituted indenyl and substituted fluorenyl includespartially saturated indenyls and fluorenyls including, but not limitedto, tetrahydroindenyls, tetrahydrofluorenyls, and octahydrofluorenyls.Exemplary alkyls that can be substituents include methyl, ethyl, propyl,butyl, pentyl, hexyl, heptyl, octyl, nonyl, or decyl, and the like.Similarly, exemplary alkenyls that can be substituents include ethenyl,propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, ordecenyl, and the like. Excluding any bridging or alkenyl linking groups,as the context requires, each substituent on X³, X⁴, X⁷, X⁸, X¹¹, X¹²,X¹⁵, X¹⁶, X¹⁹, X²⁰, X²³, and X²⁴ independently can be a hydrogen atom,or a methyl, ethyl, propyl, n-butyl, t-butyl, or hexyl group, in oneaspect of this invention.

Any substituents on A¹, A², A³, and A⁴ (other than an alkenyl linkinggroup, as the context requires) independently are a hydrogen atom, or asubstituted or unsubstituted aliphatic, aromatic, or cyclic group, or acombination thereof. In one aspect, for example, such substituentsindependently can be a methyl, ethyl, propyl, butyl, pentyl, hexyl,ethenyl, propenyl, butenyl, pentenyl, hexenyl, phenyl, naphthyl, tolyl,benzyl, cyclopentyl, cyclohexyl, or cyclohexylphenyl group, or ahydrogen atom. Excluding any alkenyl linking group, as the contextrequires, each substituent on A¹, A², A³, and A⁴ independently can be ahydrogen atom, methyl group, phenyl group, naphthyl group, orcyclohexylphenyl group, in other aspects of this invention.

In formulas (A), (B), (C), (IA)=(IB), (IIA)=(IIB), and (IIIA)=(IIIB),substituted aliphatic, aromatic, or cyclic groups, and combinationsthereof, are disclosed, as well as substituted alkyl or alkenyl groups.These groups and others described herein (e.g., hydrocarbyl) areintended to include substituted analogs with substitutions at anyposition on these groups that conform to the normal rules of chemicalvalence. Thus, groups substituted with one or more than one substituentare contemplated.

Such substituents, when present, are independently selected from anoxygen group, a sulfur group, a nitrogen group, a phosphorus group, anarsenic group, a carbon group, a silicon group, a germanium group, a tingroup, a lead group, a boron group, an aluminum group, an inorganicgroup, an organometallic group, or a substituted derivative thereof, anyof which having from 1 to about 20 carbon atoms; a halide; or hydrogen;as long as these groups do not terminate the activity of the catalystcomposition. Examples of each of these substituent groups include, butare not limited to, the following groups.

Examples of halide substituents, in each occurrence, include fluoride,chloride, bromide, and iodide.

In each occurrence, oxygen groups are oxygen-containing groups, examplesof which include, but are not limited to, alkoxy or aryloxy groups(—OR^(B)), —OSiR^(B) ₃, —OPR^(B) ₂, —OAlR^(B) ₂, and the like, includingsubstituted derivatives thereof, wherein R^(B) in each occurrence can bealkyl, cycloalkyl, aryl, aralkyl, substituted alkyl, substituted aryl,or substituted aralkyl having from 1 to 20 carbon atoms. Examples ofalkoxy or aryloxy groups (—OR^(B)) groups include, but are not limitedto, methoxy, ethoxy, propoxy, butoxy, phenoxy, substituted phenoxy, andthe like.

In each occurrence, sulfur groups are sulfur-containing groups, examplesof which include, but are not limited to, —SR^(B) and the like,including substituted derivatives thereof, wherein R^(B) in eachoccurrence can be alkyl, cycloalkyl, aryl, aralkyl, substituted alkyl,substituted aryl, or substituted aralkyl having from 1 to 20 carbonatoms.

In each occurrence, nitrogen groups are nitrogen-containing groups,which include, but are not limited to, —NR^(B) ₂ and the like, includingsubstituted derivatives thereof, wherein R^(B) in each occurrence can bealkyl, cycloalkyl, aryl, aralkyl, substituted alkyl, substituted aryl,or substituted aralkyl having from 1 to 20 carbon atoms.

In each occurrence, phosphorus groups are phosphorus-containing groups,which include, but are not limited to, —PR^(B) ₂, —P(OR^(B))₂, and thelike, including substituted derivatives thereof, wherein R^(B) in eachoccurrence can be alkyl, cycloalkyl, aryl, aralkyl, substituted alkyl,substituted aryl, or substituted aralkyl having from 1 to 20 carbonatoms.

In each occurrence, arsenic groups are arsenic-containing groups, whichinclude, but are not limited to, —AsR^(B) ₂, —As(OR^(B))₂, and the like,including substituted derivatives thereof, wherein R^(B) in eachoccurrence can be alkyl, cycloalkyl, aryl, aralkyl, substituted alkyl,substituted aryl, or substituted aralkyl having from 1 to 20 carbonatoms.

In each occurrence, carbon groups are carbon-containing groups, whichinclude, but are not limited to, alkyl halide groups that comprisehalide-substituted alkyl groups with 1 to 20 carbon atoms, aralkylgroups with 1 to 20 carbon atoms, —C(NR^(B))H, —C(NR^(B))R^(B),—C(NR^(B))OR^(B), and the like, including substituted derivativesthereof, wherein R^(B) in each occurrence can be alkyl, cycloalkyl,aryl, aralkyl, substituted alkyl, substituted aryl, or substitutedaralkyl having from 1 to 20 carbon atoms.

In each occurrence, silicon groups are silicon-containing groups, whichinclude, but are not limited to, silyl groups such as alkylsilyl groups,arylsilyl groups, arylalkylsilyl groups, siloxy groups, and the like,which in each occurrence have from 1 to 20 carbon atoms. For example,silicon group substituents include trimethylsilyl and phenyloctylsilylgroups.

In each occurrence, germanium groups are germanium-containing groups,which include, but are not limited to, germyl groups such as alkylgermylgroups, arylgermyl groups, arylalkylgermyl groups, germyloxy groups, andthe like, which in each occurrence have from 1 to 20 carbon atoms.

In each occurrence, tin groups are tin-containing groups, which include,but are not limited to, stannyl groups such as alkylstannyl groups,arylstannyl groups, arylalkylstannyl groups, stannoxy (or “stannyloxy”)groups, and the like, which in each occurrence have from 1 to 20 carbonatoms. Thus, tin groups include, but are not limited to, stannoxygroups.

In each occurrence, lead groups are lead-containing groups, whichinclude, but are not limited to, alkyllead groups, aryllead groups,arylalkyllead groups, and the like, which in each occurrence, have from1 to 20 carbon atoms.

In each occurrence, boron groups are boron-containing groups, whichinclude, but are not limited to, —BR^(B) ₂, —BX₂, —BR^(B)X, and thelike, wherein X is a monoanionic group such as hydride, alkoxide, alkylthiolate, and the like, and wherein R^(B) in each occurrence can bealkyl, cycloalkyl, aryl, aralkyl, substituted alkyl, substituted aryl,or substituted aralkyl having from 1 to 20 carbon atoms.

In each occurrence, aluminum groups are aluminum-containing groups,which include, but are not limited to, —AlR^(B), —AlX₂, —AlR^(B)X,wherein X is a monoanionic group such as hydride, alkoxide, alkylthiolate, and the like, and wherein R^(B) in each occurrence can bealkyl, cycloalkyl, aryl, aralkyl, substituted alkyl, substituted aryl,or substituted aralkyl having from 1 to 20 carbon atoms.

Examples of inorganic groups that may be used as substituents, in eachoccurrence include, but are not limited to, —OAlX₂, —OSiX₃, —OPX₂, —SX,—AsX₂, —PX₂, and the like, wherein X is a monoanionic group such ashydride, amide, alkoxide, alkyl thiolate, and the like, and wherein anyalkyl, cycloalkyl, aryl, aralkyl, substituted alkyl, substituted aryl,or substituted aralkyl group or substituent on these ligands has from 1to 20 carbon atoms.

Examples of organometallic groups that may be used as substituents, ineach occurrence, include, but are not limited to, organoboron groups,organoaluminum groups, organogallium groups, organosilicon groups,organogermanium groups, organotin groups, organolead groups,organo-transition metal groups, and the like, having from 1 to 20 carbonatoms.

The dinuclear compounds of the present invention are heteronuclear,because each metallocene moiety linked by the alkenyl linking group isdifferent, and may contain either the same or a different metal center.Accordingly, each M¹, M², M³, M⁴, M⁵, and M⁶ independently is Zr, Hf, orTi in the present invention. Often, the metal is either Zr or Hf. In theabove formulas, each E independently is carbon or silicon. Each E can becarbon in some aspects of this invention.

Each R^(X), R^(Y), and R^(Z) in the alkenyl linking group independentlyis a hydrogen atom, or a substituted or unsubstituted aliphatic,aromatic, or cyclic group, or a combination thereof. In one aspect ofthe present invention, each R^(X), R^(Y), and R^(Z) independently is asubstituted or unsubstituted aliphatic group having from 1 to 20 carbonatoms. For example, each R^(X), R^(Y), and R^(Z) independently can behydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl,nonyl, decyl, or trimethylsilylmethyl. In another aspect, each R^(X),R^(Y), and R^(Z) is a hydrogen atom.

Each R^(X), R^(Y), and R^(Z) independently is a substituted orunsubstituted aromatic group, for example, having up to 20 carbon atoms,in yet another aspect of the present invention.

Each R^(X), R^(Y), and R^(Z) independently is a methyl, ethyl, propyl,butyl, pentyl, hexyl, phenyl, naphthyl, tolyl, benzyl, cyclopentyl,cyclohexyl, or cyclohexylphenyl group, or a hydrogen atom, in otheraspects of this invention. Further, each R^(X), R^(Y), and R^(Z)independently can be methyl, phenyl, benzyl, or a hydrogen atom inanother aspect of the present invention.

The integer n in the above formulas determines the length of the alkenyllinking group and each n independently ranges from 0 to 12, inclusive.In one aspect of this invention, each n independently is equal to 0, 1,2, 3, 4, 5, or 6. In a different aspect of the present invention, each nindependently is 1, 2, 3, or 4.

An example of a heterodinuclear compound in accordance with the presentinvention is the following compound, which is abbreviated “DMET-1”throughout this disclosure:

Applicants have used the abbreviation Ph for phenyl. Anotherillustrative and non-limiting example of a heterodinuclear compound ofthe present invention includes the following compound, which isabbreviated “DMET-2” throughout this disclosure:

Methods of making a dinuclear compound of the present invention are alsoprovided. One such method for synthesizing a dinuclear metallocenecompound is illustrated in the general reaction scheme provided below:

A metallocene compound having an alkenyl substituent is linked toanother metallocene compound having an alkenyl substituent via theolefin metathesis reaction in the presence of a suitable catalyst.Generally, each alkenyl substituent can be of any length, and can be,for example, a substituent on a bridging group or a substituent on acyclopentadienyl-type group (e.g., cyclopentadienyl, indenyl,fluorenyl). In the reaction product, the metallocene moieties areconnected by an alkenyl linking group. Ethylene gas or other olefins(e.g., propylene) may be produced in this reaction.

Various metal-based catalysts can be employed in an olefin metathesisreaction. The metals often used include ruthenium, tungsten, molybdenum,and nickel. In the examples that follow, a Grubbs 1st GenerationMetathesis Catalyst based on ruthenium was employed, but this inventionis not limited to any particular metathesis catalyst.

Metathesis reactions can be conducted in the presence of a solvent suchas, for example, aliphatic, aromatic, or saturated ester solvents.Suitable solvents useful in the production of heterodinuclearmetallocene compounds include, but are not limited to, benzene, toluene,heptane, isobutane, methylene chloride, and the like. Solvent selectioncan depend upon many factors, for instance, the desired reactiontemperature and solubility of either of the metallocene reactants or theheterodinuclear metallocene in the particular solvent.

Suitable olefin metathesis reaction temperatures to produceheterodinuclear metallocene compounds of the present invention aregenerally in a range from about −50° C. to about 150° C. For example,the reaction temperature can be in the range from about 0° C. to about100° C. The reaction temperature selected is often a compromise betweenmany variables, such as the solvent employed, reaction pressure,reaction time, quantity and type of catalyst, product yield andselectivity, and isomer ratio, if desired. Further, the metathesisreaction equilibrium can be driven towards the heterodinuclearmetallocene product if ethylene gas is removed or vented from thereaction system.

Generally, there is no limitation on the selection of the metallocenecompounds that can be used to form the heterodinuclear compounds of thepresent invention, other than the presence of an alkenyl substituent ona bridging group, a cyclopentadienyl group, an indenyl group, and/or afluorenyl group. Examples of metallocene compounds that can be used toproduce heterodinuclear compounds of the present invention via theolefin metathesis reaction scheme above include, but are not limited to,those disclosed in U.S. patent application Ser. Nos. 11/965,848,11/965,982, and 11/966,081, filed on Dec. 28, 2007, the disclosures ofwhich are incorporated herein by reference in their entirety.

An illustrative and non-limiting example of two metallocene compoundsthat can be used to form a heterodinuclear compound of formula (A) isthe reaction of:

An illustrative and non-limiting example of two metallocene compoundsthat can be used to form a heterodinuclear compound of formula (B) isthe reaction of:

An illustrative and non-limiting example of two metallocene compoundsthat can be used to form a heterodinuclear compound of formula (C) isthe reaction of:

An illustrative and non-limiting example of two metallocene compoundsthat can be used to form a heterodinuclear compound of formula (IA)=(IB)is the reaction of:

An illustrative and non-limiting example of two metallocene compoundsthat can be used to form a heterodinuclear compound of formula(IIA)=(IIB) is the reaction of:

An illustrative and non-limiting example of two metallocene compoundsthat can be used to form a heterodinuclear compound of formula(IIIA)=(IIIB) is the reaction of:

Applicants have used the abbreviations Ph for phenyl, Me for methyl, andt-Bu for tert-butyl. Additional bridged and unbridged metallocenecompounds can be used to produce heterodinuclear compounds of thepresent invention. Therefore, the scope of the present invention is notlimited to the starting metallocene species provided above, nor limitedto those disclosed in U.S. patent application Ser. Nos. 11/965,848,11/965,982, and 11/966,081, which are incorporated herein by referencein their entirety.

Catalyst Composition

The present invention also relates to catalyst compositions employingheterodinuclear metallocene compounds. According to one aspect of thepresent invention, a catalyst composition is provided which comprises acontact product of a dinuclear metallocene compound and anactivator-support. This catalyst composition can further comprise anorganoaluminum compound. These catalyst compositions can be utilized toproduce polyolefins—homopolymers, copolymers, and the like—for a varietyof end-use applications. The dinuclear metallocene compound in thesecatalyst compositions can have any of the formulas (A), (B), (C),(IA)=(IB), (IIA)=(IIB), or (IIIA)=(IIIB) discussed above.

In accordance with this and other aspects of the present invention, itis contemplated that the catalyst compositions disclosed herein cancontain more than one dinuclear metallocene compound and/or more thanone activator-support. Additionally, more than one organoaluminumcompound is also contemplated. Further, one or more metallocenecompounds can be employed in the catalyst composition, in addition tothe dinuclear metallocene compound (or compounds).

In another aspect of the present invention, a catalyst composition isprovided which comprises a contact product of a dinuclear metallocenecompound, an activator-support, and an organoaluminum compound, whereinthis catalyst composition is substantially free of aluminoxanes,organoboron or organoborate compounds, and ionizing ionic compounds. Inthis aspect, the catalyst composition has catalyst activity, to bediscussed below, in the absence of these additional co-catalysts.

However, in other aspects of this invention, these co-catalysts can beemployed. For example, a catalyst composition comprising a dinuclearmetallocene compound and an activator-support can further comprise anoptional co-catalyst. Suitable co-catalysts in this aspect include, butare not limited to, aluminoxane compounds, organoboron or organoboratecompounds, ionizing ionic compounds, and the like, or any combinationthereof. More than one co-catalyst can be present in the catalystcomposition.

In a different aspect, a catalyst composition is provided which does notrequire an activator-support. Such a catalyst composition comprises thecontact product of a dinuclear metallocene compound and an aluminoxanecompound, an organoboron or organoborate compound, an ionizing ioniccompound, or combinations thereof. In this aspect, the dinuclearmetallocene compound has the formula (A), (B), (C), (IA)=(IB),(IIA)=(IIB), or (IIIA)=(IIIB).

Activator-Support

The present invention encompasses various catalyst compositionscontaining an activator, which can be an activator-support. In oneaspect, the activator-support comprises a chemically-treated solidoxide. Alternatively, the activator-support can comprise a clay mineral,a pillared clay, an exfoliated clay, an exfoliated clay gelled intoanother oxide matrix, a layered silicate mineral, a non-layered silicatemineral, a layered aluminosilicate mineral, a non-layeredaluminosilicate mineral, or any combination thereof. Generally, theactivator-support contains Brønsted or Lewis acid groups.

Generally, chemically-treated solid oxides exhibit enhanced acidity ascompared to the corresponding untreated solid oxide compound. Thechemically-treated solid oxide also functions as a catalyst activator ascompared to the corresponding untreated solid oxide. While thechemically-treated solid oxide activates the dinuclear metallocene inthe absence of co-catalysts, it is not necessary to eliminateco-catalysts from the catalyst composition. The activation function ofthe activator-support is evident in the enhanced activity of catalystcomposition as a whole, as compared to a catalyst composition containingthe corresponding untreated solid oxide. However, it is believed thatthe chemically-treated solid oxide can function as an activator, even inthe absence of an organoaluminum compound, aluminoxanes, organoboron ororganoborate compounds, ionizing ionic compounds, and the like.

The chemically-treated solid oxide can comprise a solid oxide treatedwith an electron-withdrawing anion. While not intending to be bound bythe following statement, it is believed that treatment of the solidoxide with an electron-withdrawing component augments or enhances theacidity of the oxide. Thus, either the activator-support exhibits Lewisor Brønsted acidity that is typically greater than the Lewis or Brønstedacid strength of the untreated solid oxide, or the activator-support hasa greater number of acid sites than the untreated solid oxide, or both.One method to quantify the acidity of the chemically-treated anduntreated solid oxide materials is by comparing the polymerizationactivities of the treated and untreated oxides under acid catalyzedreactions.

Chemically-treated solid oxides of this invention are formed generallyfrom an inorganic solid oxide that exhibits Lewis acidic or Brønstedacidic behavior and has a relatively high porosity. The solid oxide ischemically-treated with an electron-withdrawing component, typically anelectron-withdrawing anion, to form an activator-support.

According to one aspect of the present invention, the solid oxide usedto prepare the chemically-treated solid oxide has a pore volume greaterthan about 0.1 cc/g. According to another aspect of the presentinvention, the solid oxide has a pore volume greater than about 0.5cc/g. According to yet another aspect of the present invention, thesolid oxide has a pore volume greater than about 1.0 cc/g.

In another aspect, the solid oxide has a surface area of from about 100to about 1000 m²/g. In yet another aspect, the solid oxide has a surfacearea of from about 200 to about 800 m²/g. In still another aspect of thepresent invention, the solid oxide has a surface area of from about 250to about 600 m²/g.

The chemically-treated solid oxide can comprise a solid inorganic oxidecomprising oxygen and one or more elements selected from Group 2, 3, 4,5, 6, 7, 8, 9, 10, 11, 12, 13, 14, or 15 of the periodic table, orcomprising oxygen and one or more elements selected from the lanthanideor actinide elements (See: Hawley's Condensed Chemical Dictionary,11^(th) Ed., John Wiley & Sons, 1995; Cotton, F. A., Wilkinson, G.,Murillo; C. A., and Bochmann, M., Advanced Inorganic Chemistry, 6^(th)Ed., Wiley-Interscience, 1999). For example, the inorganic oxide cancomprise oxygen and an element, or elements, selected from Al, B, Be,Bi, Cd, Co, Cr, Cu, Fe, Ga, La, Mn, Mo, Ni, Sb, Si, Sn, Sr, Th, Ti, V,W, P, Y, Zn, and Zr.

Suitable examples of solid oxide materials or compounds that can be usedto form the chemically-treated solid oxide include, but are not limitedto, Al₂O₃, B₂O₃, BeO, Bi₂O₃, CdO, CO₃O₄, Cr₂O₃, CuO, Fe₂O₃, Ga₂O₃,La₂O₃, Mn₂O₃, MoO₃, NiO, P₂O₅, Sb₂O₅, SiO₂, SnO₂, SrO, ThO₂, TiO₂, V₂O₅,WO₃, Y₂O₃, ZnO, ZrO₂, and the like, including mixed oxides thereof, andcombinations thereof. For example, the solid oxide can comprise silica,alumina, silica-alumina, aluminum phosphate, heteropolytungstate,titania, zirconia, magnesia, boria, zinc oxide, mixed oxides thereof, orany combination thereof.

The solid oxide of this invention encompasses oxide materials such asalumina, “mixed oxide” compounds thereof such as silica-alumina, andcombinations and mixtures thereof. The mixed oxide compounds such assilica-alumina can be single or multiple chemical phases with more thanone metal combined with oxygen to form a solid oxide compound. Examplesof mixed oxides that can be used in the activator-support of the presentinvention include, but are not limited to, silica-alumina,silica-titania, silica-zirconia, zeolites, various clay minerals,alumina-titania, alumina-zirconia, zinc-aluminate, and the like.

The electron-withdrawing component used to treat the solid oxide can beany component that increases the Lewis or Brønsted acidity of the solidoxide upon treatment (as compared to the solid oxide that is not treatedwith at least one electron-withdrawing anion). According to one aspectof the present invention, the electron-withdrawing component is anelectron-withdrawing anion derived from a salt, an acid, or othercompound, such as a volatile organic compound, that serves as a sourceor precursor for that anion. Examples of electron-withdrawing anionsinclude, but are not limited to, sulfate, bisulfate, fluoride, chloride,bromide, iodide, fluorosulfate, fluoroborate, phosphate,fluorophosphate, trifluoroacetate, triflate, fluorozirconate,fluorotitanate, and the like, including mixtures and combinationsthereof. In addition, other ionic or non-ionic compounds that serve assources for these electron-withdrawing anions also can be employed inthe present invention. It is contemplated that the electron-withdrawinganion can be, or can comprise, fluoride, chloride, bromide, phosphate,triflate, bisulfate, or sulfate, and the like, or any combinationthereof, in some aspects of this invention.

Thus, for example, the chemically-treated solid oxide used in thecatalyst compositions of the present invention can be, or can comprise,fluorided alumina, chlorided alumina, bromided alumina, sulfatedalumina, fluorided silica-alumina, chlorided silica-alumina, bromidedsilica-alumina, sulfated silica-alumina, fluorided silica-zirconia,chlorided silica-zirconia, bromided silica-zirconia, sulfatedsilica-zirconia, fluorided silica-titania, fluorided silica-cladalumina, and the like, or combinations thereof.

When the electron-withdrawing component comprises a salt of anelectron-withdrawing anion, the counterion or cation of that salt can beselected from any cation that allows the salt to revert or decomposeback to the acid during calcining. Factors that dictate the suitabilityof the particular salt to serve as a source for the electron-withdrawinganion include, but are not limited to, the solubility of the salt in thedesired solvent, the lack of adverse reactivity of the cation,ion-pairing effects between the cation and anion, hygroscopic propertiesimparted to the salt by the cation, and the like, and thermal stabilityof the anion. Examples of suitable cations in the salt of theelectron-withdrawing anion include, but are not limited to, ammonium,trialkyl ammonium, tetraalkyl ammonium, tetraalkyl phosphonium, H⁺,[H(OEt₂)₂]⁺, and the like.

Further, combinations of one or more different electron-withdrawinganions, in varying proportions, can be used to tailor the specificacidity of the activator-support to the desired level. Combinations ofelectron-withdrawing components can be contacted with the oxide materialsimultaneously or individually, and in any order that affords thedesired chemically-treated solid oxide acidity. For example, one aspectof this invention is employing two or more electron-withdrawing anionsource compounds in two or more separate contacting steps.

Thus, one example of such a process by which a chemically-treated solidoxide is prepared is as follows: a selected solid oxide, or combinationof solid oxides, is contacted with a first electron-withdrawing anionsource compound to form a first mixture; this first mixture is calcinedand then contacted with a second electron-withdrawing anion sourcecompound to form a second mixture; the second mixture is then calcinedto form a treated solid oxide. In such a process, the first and secondelectron-withdrawing anion source compounds can be either the same ordifferent compounds.

According to another aspect of the present invention, thechemically-treated solid oxide comprises a solid inorganic oxidematerial, a mixed oxide material, or a combination of inorganic oxidematerials, that is chemically-treated with an electron-withdrawingcomponent, and optionally treated with a metal source, including metalsalts, metal ions, or other metal-containing compounds. Non-limitingexamples of the metal or metal ion include zinc, nickel, vanadium,titanium, silver, copper, gallium, tin, tungsten, molybdenum, zirconium,and the like, or combinations thereof. Examples of chemically-treatedsolid oxides that contain a metal or metal ion include, but are notlimited to, zinc-impregnated chlorided alumina, titanium-impregnatedfluorided alumina, zinc-impregnated fluorided alumina, zinc-impregnatedchlorided silica-alumina, zinc-impregnated fluorided silica-alumina,zinc-impregnated sulfated alumina, chlorided zinc aluminate, fluoridedzinc aluminate, sulfated zinc aluminate, silica-clad alumina treatedwith hexafluorotitanic acid, silica-clad alumina treated with zinc andthen fluorided, and the like, or any combination thereof.

Any method of impregnating the solid oxide material with a metal can beused. The method by which the oxide is contacted with a metal source,typically a salt or metal-containing compound, can include, but is notlimited to, gelling, co-gelling, impregnation of one compound ontoanother, and the like. If desired, the metal-containing compound isadded to or impregnated into the solid oxide in solution form, andsubsequently converted into the supported metal upon calcining.Accordingly, the solid inorganic oxide can further comprise a metalselected from zinc, titanium, nickel, vanadium, silver, copper, gallium,tin, tungsten, molybdenum, and the like, or combinations of thesemetals. For example, zinc is often used to impregnate the solid oxidebecause it can provide improved catalyst activity at a low cost.

The solid oxide can be treated with metal salts or metal-containingcompounds before, after, or at the same time that the solid oxide istreated with the electron-withdrawing anion. Following any contactingmethod, the contacted mixture of solid compound, electron-withdrawinganion, and the metal ion is typically calcined. Alternatively, a solidoxide material, an electron-withdrawing anion source, and the metal saltor metal-containing compound are contacted and calcined simultaneously.

Various processes are used to form the chemically-treated solid oxideuseful in the present invention. The chemically-treated solid oxide cancomprise the contact product of one or more solid oxides with one ormore electron-withdrawing anion sources. It is not required that thesolid oxide be calcined prior to contacting the electron-withdrawinganion source. The contact product typically is calcined either during orafter the solid oxide is contacted with the electron-withdrawing anionsource. The solid oxide can be calcined or uncalcined. Various processesto prepare solid oxide activator-supports that can be employed in thisinvention have been reported. For example, such methods are described inU.S. Pat. Nos. 6,107,230, 6,165,929, 6,294,494, 6,300,271, 6,316,553,6,355,594, 6,376,415, 6,388,017, 6,391,816, 6,395,666, 6,524,987,6,548,441, 6,548,442, 6,576,583, 6,613,712, 6,632,894, 6,667,274, and6,750,302, the disclosures of which are incorporated herein by referencein their entirety.

According to one aspect of the present invention, the solid oxidematerial is chemically-treated by contacting it with anelectron-withdrawing component, typically an electron-withdrawing anionsource. Further, the solid oxide material optionally is chemicallytreated with a metal ion, and then calcined to form a metal-containingor metal-impregnated chemically-treated solid oxide. According toanother aspect of the present invention, the solid oxide material andelectron-withdrawing anion source are contacted and calcinedsimultaneously.

The method by which the oxide is contacted with the electron-withdrawingcomponent, typically a salt or an acid of an electron-withdrawing anion,can include, but is not limited to, gelling, co-gelling, impregnation ofone compound onto another, and the like. Thus, following any contactingmethod, the contacted mixture of the solid oxide, electron-withdrawinganion, and optional metal ion, is calcined.

The solid oxide activator-support (i.e., chemically-treated solid oxide)thus can be produced by a process comprising:

1) contacting a solid oxide (or solid oxides) with anelectron-withdrawing anion source compound (or compounds) to form afirst mixture; and

2) calcining the first mixture to form the solid oxideactivator-support.

According to another aspect of the present invention, the solid oxideactivator-support (chemically-treated solid oxide) is produced by aprocess comprising:

1) contacting a solid oxide (or solid oxides) with a firstelectron-withdrawing anion source compound to form a first mixture;

2) calcining the first mixture to produce a calcined first mixture;

3) contacting the calcined first mixture with a secondelectron-withdrawing anion source compound to form a second mixture; and

4) calcining the second mixture to form the solid oxideactivator-support.

According to yet another aspect of the present invention, thechemically-treated solid oxide is produced or formed by contacting thesolid oxide with the electron-withdrawing anion source compound, wherethe solid oxide compound is calcined before, during, or after contactingthe electron-withdrawing anion source, and where there is a substantialabsence of aluminoxanes, organoboron or organoborate compounds, andionizing ionic compounds.

Calcining of the treated solid oxide generally is conducted in anambient atmosphere, typically in a dry ambient atmosphere, at atemperature from about 200° C. to about 900° C., and for a time of about1 minute to about 100 hours. Calcining can be conducted at a temperatureof from about 300° C. to about 800° C., or alternatively, at atemperature of from about 400° C. to about 700° C. Calcining can beconducted for about 30 minutes to about 50 hours, or for about 1 hour toabout 15 hours. Thus, for example, calcining can be carried out forabout 1 to about 10 hours at a temperature of from about 350° C. toabout 550° C. Any suitable ambient atmosphere can be employed duringcalcining. Generally, calcining is conducted in an oxidizing atmosphere,such as air. Alternatively, an inert atmosphere, such as nitrogen orargon, or a reducing atmosphere, such as hydrogen or carbon monoxide,can be used.

According to one aspect of the present invention, the solid oxidematerial is treated with a source of halide ion, sulfate ion, or acombination of anions, optionally treated with a metal ion, and thencalcined to provide the chemically-treated solid oxide in the form of aparticulate solid. For example, the solid oxide material can be treatedwith a source of sulfate (termed a “sulfating agent”), a source ofchloride ion (termed a “chloriding agent”), a source of fluoride ion(termed a “fluoriding agent”), or a combination thereof, and calcined toprovide the solid oxide activator. Useful acidic activator-supportsinclude, but are not limited to, bromided alumina, chlorided alumina,fluorided alumina, sulfated alumina, bromided silica-alumina, chloridedsilica-alumina, fluorided silica-alumina, sulfated silica-alumina,bromided silica-zirconia, chlorided silica-zirconia, fluoridedsilica-zirconia, sulfated silica-zirconia, fluorided silica-titania,alumina treated with hexafluorotitanic acid, silica-clad alumina treatedwith hexafluorotitanic acid, silica-alumina treated withhexafluorozirconic acid, fluorided boria-alumina, silica treated withtetrafluoroboric acid, alumina treated with tetrafluoroboric acid,alumina treated with hexafluorophosphoric acid, a pillared clay, such asa pillared montmorillonite, optionally treated with fluoride, chloride,or sulfate; phosphated alumina or other aluminophosphates optionallytreated with sulfate, fluoride, or chloride; or any combination of theabove. Further, any of these activator-supports optionally can betreated with a metal ion.

The chemically-treated solid oxide can comprise a fluorided solid oxidein the form of a particulate solid. The fluorided solid oxide can beformed by contacting a solid oxide with a fluoriding agent. The fluorideion can be added to the oxide by forming a slurry of the oxide in asuitable solvent such as alcohol or water including, but not limited to,the one to three carbon alcohols because of their volatility and lowsurface tension. Examples of suitable fluoriding agents include, but arenot limited to, hydrofluoric acid (HF), ammonium fluoride (NH₄F),ammonium bifluoride (NH₄HF₂), ammonium tetrafluoroborate (NH₄BF₄),ammonium silicofluoride (hexafluorosilicate) ((NH₄)₂SiF₆), ammoniumhexafluorophosphate (NH₄ PF₆), hexafluorotitanic acid (H₂TiF₆), ammoniumhexafluorotitanic acid ((NH₄)₂TiF₆), hexafluorozirconic acid (H₂ZrF₆),analogs thereof, and combinations thereof. For example, ammoniumbifluoride NH₄HF₂ can be used as the fluoriding agent, due to its easeof use and availability.

If desired, the solid oxide is treated with a fluoriding agent duringthe calcining step. Any fluoriding agent capable of thoroughlycontacting the solid oxide during the calcining step can be used. Forexample, in addition to those fluoriding agents described previously,volatile organic fluoriding agents can be used. Examples of volatileorganic fluoriding agents useful in this aspect of the inventioninclude, but are not limited to, freons, perfluorohexane,perfluorobenzene, fluoromethane, trifluoroethanol, an the like, andcombinations thereof. Gaseous hydrogen fluoride or fluorine itself alsocan be used with the solid oxide if fluorided while calcining. Silicontetrafluoride (SiF₄) and compounds containing tetrafluoroborate (BF₄)also can be employed. One convenient method of contacting the solidoxide with the fluoriding agent is to vaporize a fluoriding agent into agas stream used to fluidize the solid oxide during calcination.

Similarly, in another aspect of this invention, the chemically-treatedsolid oxide comprises a chlorided solid oxide in the form of aparticulate solid. The chlorided solid oxide is formed by contacting asolid oxide with a chloriding agent. The chloride ion can be added tothe oxide by forming a slurry of the oxide in a suitable solvent. Thesolid oxide can be treated with a chloriding agent during the calciningstep. Any chloriding agent capable of serving as a source of chlorideand thoroughly contacting the oxide during the calcining step can beused. For example, volatile organic chloriding agents can be used.Examples of suitable volatile organic chloriding agents include, but arenot limited to, certain freons, perchlorobenzene, chloromethane,dichloromethane, chloroform, carbon tetrachloride, trichloroethanol, andthe like, or any combination thereof. Gaseous hydrogen chloride orchlorine itself also can be used with the solid oxide during calciningOne convenient method of contacting the oxide with the chloriding agentis to vaporize a chloriding agent into a gas stream used to fluidize thesolid oxide during calcination.

The amount of fluoride or chloride ion present before calcining thesolid oxide generally is from about 1 to about 50% by weight, where theweight percent is based on the weight of the solid oxide, for example,silica-alumina, before calcining. According to another aspect of thisinvention, the amount of fluoride or chloride ion present beforecalcining the solid oxide is from about 1 to about 25% by weight, andaccording to another aspect of this invention, from about 2 to about 20%by weight. According to yet another aspect of this invention, the amountof fluoride or chloride ion present before calcining the solid oxide isfrom about 4 to about 10% by weight. Once impregnated with halide, thehalided oxide can be dried by any suitable method including, but notlimited to, suction filtration followed by evaporation, drying undervacuum, spray drying, and the like, although it is also possible toinitiate the calcining step immediately without drying the impregnatedsolid oxide.

The silica-alumina used to prepare the treated silica-alumina typicallyhas a pore volume greater than about 0.5 cc/g. According to one aspectof the present invention, the pore volume is greater than about 0.8cc/g, and according to another aspect of the present invention, greaterthan about 1.0 cc/g. Further, the silica-alumina generally has a surfacearea greater than about 100 m²/g. According to another aspect of thisinvention, the surface area is greater than about 250 m²/g. Yet, inanother aspect, the surface area is greater than about 350 m²/g.

The silica-alumina utilized in the present invention typically has analumina content from about 5 to about 95% by weight. According to oneaspect of this invention, the alumina content of the silica-alumina isfrom about 5 to about 50%, or from about 8% to about 30%, alumina byweight. In another aspect, high alumina content silica-alumina compoundscan employed, in which the alumina content of these silica-aluminacompounds typically ranges from about 60% to about 90%, or from about65% to about 80%, alumina by weight. According to yet another aspect ofthis invention, the solid oxide component comprises alumina withoutsilica, and according to another aspect of this invention, the solidoxide component comprises silica without alumina.

The sulfated solid oxide comprises sulfate and a solid oxide component,such as alumina or silica-alumina, in the form of a particulate solid.Optionally, the sulfated oxide is treated further with a metal ion suchthat the calcined sulfated oxide comprises a metal. According to oneaspect of the present invention, the sulfated solid oxide comprisessulfate and alumina. In some instances, the sulfated alumina is formedby a process wherein the alumina is treated with a sulfate source, forexample, sulfuric acid or a sulfate salt such as ammonium sulfate. Thisprocess is generally performed by forming a slurry of the alumina in asuitable solvent, such as alcohol or water, in which the desiredconcentration of the sulfating agent has been added. Suitable organicsolvents include, but are not limited to, the one to three carbonalcohols because of their volatility and low surface tension.

According to one aspect of this invention, the amount of sulfate ionpresent before calcining is from about 0.5 to about 100 parts by weightsulfate ion to about 100 parts by weight solid oxide. According toanother aspect of this invention, the amount of sulfate ion presentbefore calcining is from about 1 to about 50 parts by weight sulfate ionto about 100 parts by weight solid oxide, and according to still anotheraspect of this invention, from about 5 to about 30 parts by weightsulfate ion to about 100 parts by weight solid oxide. These weightratios are based on the weight of the solid oxide before calcining Onceimpregnated with sulfate, the sulfated oxide can be dried by anysuitable method including, but not limited to, suction filtrationfollowed by evaporation, drying under vacuum, spray drying, and thelike, although it is also possible to initiate the calcining stepimmediately.

According to another aspect of the present invention, theactivator-support used in preparing the catalyst compositions of thisinvention comprises an ion-exchangeable activator-support, including butnot limited to silicate and aluminosilicate compounds or minerals,either with layered or non-layered structures, and combinations thereof.In another aspect of this invention, ion-exchangeable, layeredaluminosilicates such as pillared clays are used as activator-supports.When the acidic activator-support comprises an ion-exchangeableactivator-support, it can optionally be treated with at least oneelectron-withdrawing anion such as those disclosed herein, thoughtypically the ion-exchangeable activator-support is not treated with anelectron-withdrawing anion.

According to another aspect of the present invention, theactivator-support of this invention comprises clay minerals havingexchangeable cations and layers capable of expanding. Typical claymineral activator-supports include, but are not limited to,ion-exchangeable, layered aluminosilicates such as pillared clays.Although the term “support” is used, it is not meant to be construed asan inert component of the catalyst composition, but rather is to beconsidered an active part of the catalyst composition, because of itsintimate association with the metallocene component.

According to another aspect of the present invention, the clay materialsof this invention encompass materials either in their natural state orthat have been treated with various ions by wetting, ion exchange, orpillaring. Typically, the clay material activator-support of thisinvention comprises clays that have been ion exchanged with largecations, including polynuclear, highly charged metal complex cations.However, the clay material activator-supports of this invention alsoencompass clays that have been ion exchanged with simple salts,including, but not limited to, salts of Al(III), Fe(II), Fe(III), andZn(II) with ligands such as halide, acetate, sulfate, nitrate, ornitrite.

According to another aspect of the present invention, theactivator-support comprises a pillared clay. The term “pillared clay” isused to refer to clay materials that have been ion exchanged with large,typically polynuclear, highly charged metal complex cations. Examples ofsuch ions include, but are not limited to, Keggin ions which can havecharges such as 7+, various polyoxometallates, and other large ions.Thus, the term pillaring refers to a simple exchange reaction in whichthe exchangeable cations of a clay material are replaced with large,highly charged ions, such as Keggin ions. These polymeric cations arethen immobilized within the interlayers of the clay and when calcinedare converted to metal oxide “pillars,” effectively supporting the claylayers as column-like structures. Thus, once the clay is dried andcalcined to produce the supporting pillars between clay layers, theexpanded lattice structure is maintained and the porosity is enhanced.The resulting pores can vary in shape and size as a function of thepillaring material and the parent clay material used. Examples ofpillaring and pillared clays are found in: T. J. Pinnavaia, Science 220(4595), 365-371 (1983); J. M. Thomas, Intercalation Chemistry, (S.Whittington and A. Jacobson, eds.) Ch. 3, pp. 55-99, Academic Press,Inc., (1972); U.S. Pat. No. 4,452,910; U.S. Pat. No. 5,376,611; and U.S.Pat. No. 4,060,480; the disclosures of which are incorporated herein byreference in their entirety.

The pillaring process utilizes clay minerals having exchangeable cationsand layers capable of expanding. Any pillared clay that can enhance thepolymerization of olefins in the catalyst composition of the presentinvention can be used. Therefore, suitable clay minerals for pillaringinclude, but are not limited to, allophanes; smectites, bothdioctahedral (Al) and tri-octahedral (Mg) and derivatives thereof suchas montmorillonites (bentonites), nontronites, hectorites, or laponites;halloysites; vermiculites; micas; fluoromicas; chlorites; mixed-layerclays; the fibrous clays including but not limited to sepiolites,attapulgites, and palygorskites; a serpentine clay; illite; laponite;saponite; and any combination thereof. In one aspect, the pillared clayactivator-support comprises bentonite or montmorillonite. The principalcomponent of bentonite is montmorillonite.

The pillared clay can be pretreated if desired. For example, a pillaredbentonite is pretreated by drying at about 300° C. under an inertatmosphere, typically dry nitrogen, for about 3 hours, before beingadded to the polymerization reactor. Although an exemplary pretreatmentis described herein, it should be understood that the preheating can becarried out at many other temperatures and times, including anycombination of temperature and time steps, all of which are encompassedby this invention.

The activator-support used to prepare the catalyst compositions of thepresent invention can be combined with other inorganic supportmaterials, including, but not limited to, zeolites, inorganic oxides,phosphated inorganic oxides, and the like. In one aspect, typicalsupport materials that are used include, but are not limited to, silica,silica-alumina, alumina, titania, zirconia, magnesia, boria, thoria,aluminophosphate, aluminum phosphate, silica-titania, coprecipitatedsilica/titania, mixtures thereof, or any combination thereof.

According to another aspect of the present invention, one or more of thedinuclear metallocene compounds can be precontacted with an olefinmonomer and an organoaluminum compound for a first period of time priorto contacting this mixture with the activator-support. Once theprecontacted mixture of the metallocene compound(s), olefin monomer, andorganoaluminum compound is contacted with the activator-support, thecomposition further comprising the activator-support is termed a“postcontacted” mixture. The postcontacted mixture can be allowed toremain in further contact for a second period of time prior to beingcharged into the reactor in which the polymerization process will becarried out.

According to yet another aspect of the present invention, one or more ofthe dinuclear metallocene compounds can be precontacted with an olefinmonomer and an activator-support for a first period of time prior tocontacting this mixture with the organoaluminum compound. Once theprecontacted mixture of the metallocene compound(s), olefin monomer, andactivator-support is contacted with the organoaluminum compound, thecomposition further comprising the organoaluminum is termed a“postcontacted” mixture. The postcontacted mixture can be allowed toremain in further contact for a second period of time prior to beingintroduced into the polymerization reactor.

Organoaluminum Compounds

In one aspect, catalyst compositions of the present invention cancomprise organoaluminum compounds. Such compounds include, but are notlimited to, compounds having the formula:

(R^(C))₃Al;

where R^(C) is an aliphatic group having from 2 to 10 carbon atoms. Forexample, R^(C) can be ethyl, propyl, butyl, hexyl, or isobutyl.

Other organoaluminum compounds which can be used in catalystcompositions disclosed herein can include, but are not limited to,compounds having the formula:

Al(X²⁵)_(m)(X²⁶)_(3-m),

where X²⁵ is a hydrocarbyl; X²⁶ is an alkoxide or an aryloxide, ahalide, or a hydride; and m is from 1 to 3, inclusive. Hydrocarbyl isused herein to specify a hydrocarbon radical group and includes, but isnot limited to, aryl, alkyl, cycloalkyl, alkenyl, cycloalkenyl,cycloalkadienyl, alkynyl, aralkyl, aralkenyl, aralkynyl, and the like,and includes all substituted, unsubstituted, branched, linear, and/orheteroatom substituted derivatives thereof.

In one aspect, X²⁵ is a hydrocarbyl having from 1 to about 20 carbonatoms. In another aspect of the present invention, X²⁵ is an alkylhaving from 1 to 10 carbon atoms. For example, X²⁵ can be ethyl, propyl,n-butyl, sec-butyl, isobutyl, or hexyl, and the like, in yet anotheraspect of the present invention.

According to one aspect of the present invention, X²⁶ is an alkoxide oran aryloxide, any one of which has from 1 to 20 carbon atoms, a halide,or a hydride. In another aspect of the present invention, X²⁶ isselected independently from fluorine or chlorine. Yet, in anotheraspect, X²⁶ is chlorine.

In the formula, Al(X²⁵)_(m)(X²⁶)_(3-m), m is a number from 1 to 3,inclusive, and typically, m is 3. The value of m is not restricted to bean integer; therefore, this formula includes sesquihalide compounds orother organoaluminum cluster compounds.

Examples of organoaluminum compounds suitable for use in accordance withthe present invention include, but are not limited to, trialkylaluminumcompounds, dialkylaluminum halide compounds, dialkylaluminum alkoxidecompounds, dialkylaluminum hydride compounds, and combinations thereof.Specific non-limiting examples of suitable organoaluminum compoundsinclude trimethylaluminum (TMA), triethylaluminum (TEA),tri-n-propylaluminum (TNPA), tri-n-butylaluminum (TNBA),triisobutylaluminum (TIBA), tri-n-hexylaluminum, tri-n-octylaluminum,diisobutylaluminum hydride, diethylaluminum ethoxide, diethylaluminumchloride, and the like, or combinations thereof.

The present invention contemplates a method of precontacting a dinuclearmetallocene compound with an organoaluminum compound and an olefinmonomer to form a precontacted mixture, prior to contacting thisprecontacted mixture with an activator-support to form a catalystcomposition. When the catalyst composition is prepared in this manner,typically, though not necessarily, a portion of the organoaluminumcompound is added to the precontacted mixture and another portion of theorganoaluminum compound is added to the postcontacted mixture preparedwhen the precontacted mixture is contacted with the solid oxideactivator-support. However, the entire organoaluminum compound can beused to prepare the catalyst composition in either the precontacting orpostcontacting step. Alternatively, all the catalyst components arecontacted in a single step.

Further, more than one organoaluminum compound can be used in either theprecontacting or the postcontacting step. When an organoaluminumcompound is added in multiple steps, the amounts of organoaluminumcompound disclosed herein include the total amount of organoaluminumcompound used in both the precontacted and postcontacted mixtures, andany additional organoaluminum compound added to the polymerizationreactor. Therefore, total amounts of organoaluminum compounds aredisclosed regardless of whether a single organoaluminum compound or morethan one organoaluminum compound is used.

Aluminoxane Compounds

The present invention further provides a catalyst composition which cancomprise an aluminoxane compound. As used herein, the term “aluminoxane”refers to aluminoxane compounds, compositions, mixtures, or discretespecies, regardless of how such aluminoxanes are prepared, formed orotherwise provided. For example, a catalyst composition comprising analuminoxane compound can be prepared in which aluminoxane is provided asthe poly(hydrocarbyl aluminum oxide), or in which aluminoxane isprovided as the combination of an aluminum alkyl compound and a sourceof active protons such as water. Aluminoxanes are also referred to aspoly(hydrocarbyl aluminum oxides) or organoaluminoxanes.

The other catalyst components typically are contacted with thealuminoxane in a saturated hydrocarbon compound solvent, though anysolvent that is substantially inert to the reactants, intermediates, andproducts of the activation step can be used. The catalyst compositionformed in this manner is collected by any suitable method, for example,by filtration. Alternatively, the catalyst composition is introducedinto the polymerization reactor without being isolated.

The aluminoxane compound of this invention can be an oligomeric aluminumcompound comprising linear structures, cyclic structures, or cagestructures, or mixtures of all three. Cyclic aluminoxane compoundshaving the formula:

wherein R is a linear or branched alkyl having from 1 to 10 carbonatoms, and p is an integer from 3 to 20, are encompassed by thisinvention. The AlRO moiety shown here also constitutes the repeatingunit in a linear aluminoxane. Thus, linear aluminoxanes having theformula:

wherein R is a linear or branched alkyl having from 1 to 10 carbonatoms, and q is an integer from 1 to 50, are also encompassed by thisinvention.

Further, aluminoxanes can have cage structures of the formula R^(t)_(5r+α)R^(b) _(r−α)Al_(4r)O_(3r), wherein R^(t) is a terminal linear orbranched alkyl group having from 1 to 10 carbon atoms; R^(b) is abridging linear or branched alkyl group having from 1 to 10 carbonatoms; r is 3 or 4; and α is equal to n_(Al(3))−n_(O(2))+n_(O(4)),wherein n_(Al(3)) is the number of three coordinate aluminum atoms,n_(o(2)) is the number of two coordinate oxygen atoms, and n_(O(4)) isthe number of 4 coordinate oxygen atoms.

Thus, aluminoxanes which can be employed in the catalyst compositions ofthe present invention are represented generally by formulas such as(R—Al—O)_(p), R(R—Al—O)_(q)AlR₂, and the like. In these formulas, the Rgroup is typically a linear or branched C₁-C₆ alkyl, such as methyl,ethyl, propyl, butyl, pentyl, or hexyl. Examples of aluminoxanecompounds that can be used in accordance with the present inventioninclude, but are not limited to, methylaluminoxane, ethylaluminoxane,n-propylaluminoxane, is o-propylaluminoxane, n-butylaluminoxane,t-butyl-aluminoxane, sec-butylaluminoxane, iso-butylaluminoxane,1-pentylaluminoxane, 2-pentylaluminoxane, 3-pentylaluminoxane,isopentylaluminoxane, neopentylaluminoxane, and the like, or anycombination thereof. Methylaluminoxane, ethylaluminoxane, andiso-butylaluminoxane are prepared from trimethylaluminum,triethylaluminum, or triisobutylaluminum, respectively, and sometimesare referred to as poly(methyl aluminum oxide), poly(ethyl aluminumoxide), and poly(isobutyl aluminum oxide), respectively. It is alsowithin the scope of the invention to use an aluminoxane in combinationwith a trialkylaluminum, such as that disclosed in U.S. Pat. No.4,794,096, incorporated herein by reference in its entirety.

The present invention contemplates many values of p and q in thealuminoxane formulas (R—Al—O)_(p) and R(R—Al—O)_(q)AlR₂, respectively.In some aspects, p and q are at least 3. However, depending upon how theorganoaluminoxane is prepared, stored, and used, the value of p and qcan vary within a single sample of aluminoxane, and such combinations oforganoaluminoxanes are contemplated herein.

In preparing a catalyst composition containing an aluminoxane, the molarratio of the total moles of aluminum in the aluminoxane (oraluminoxanes) to the total moles of dinuclear metallocene compound (orcompounds, including metallocene compounds) in the composition isgenerally between about 1:10 and about 100,000:1. In another aspect, themolar ratio is in a range from about 5:1 to about 15,000:1. Optionally,aluminoxane can be added to a polymerization zone in ranges from about0.01 mg/L to about 1000 mg/L, from about 0.1 mg/L to about 100 mg/L, orfrom about 1 mg/L to about 50 mg/L.

Organoaluminoxanes can be prepared by various procedures. Examples oforganoaluminoxane preparations are disclosed in U.S. Pat. Nos. 3,242,099and 4,808,561, the disclosures of which are incorporated herein byreference in their entirety. For example, water in an inert organicsolvent can be reacted with an aluminum alkyl compound, such as(R^(C))₃Al, to form the desired organoaluminoxane compound. While notintending to be bound by this statement, it is believed that thissynthetic method can afford a mixture of both linear and cyclic R—Al—Oaluminoxane species, both of which are encompassed by this invention.Alternatively, organoaluminoxanes are prepared by reacting an aluminumalkyl compound, such as (R^(C))₃Al with a hydrated salt, such ashydrated copper sulfate, in an inert organic solvent.

Organoboron/Organoborate Compounds

According to another aspect of the present invention, a catalystcomposition comprising organoboron or organoborate compounds isprovided. Such compounds include neutral boron compounds, borate salts,and the like, or combinations thereof. For example, fluoroorgano boroncompounds and fluoroorgano borate compounds are contemplated.

Any fluoroorgano boron or fluoroorgano borate compound can be utilizedwith the present invention. Examples of fluoroorgano borate compoundsthat can be used in the present invention include, but are not limitedto, fluorinated aryl borates such as N,N-dimethylaniliniumtetrakis(pentafluorophenyl)borate, triphenylcarbeniumtetrakis(pentafluorophenyl)borate, lithiumtetrakis(pentafluorophenyl)borate, N,N-dimethylaniliniumtetrakis[3,5-bis(trifluoromethyl)phenyl]borate, triphenylcarbeniumtetrakis[3,5-bis(trifluoromethyl)phenyl]borate, and the like, ormixtures thereof. Examples of fluoroorgano boron compounds that can beused as co-catalysts in the present invention include, but are notlimited to, tris(pentafluorophenyl)boron,tris[3,5-bis(trifluoromethyl)phenyl]boron, and the like, or mixturesthereof. Although not intending to be bound by the following theory,these examples of fluoroorgano borate and fluoroorgano boron compounds,and related compounds, are thought to form “weakly-coordinating” anionswhen combined with organometal or metallocene compounds, as disclosed inU.S. Pat. No. 5,919,983, the disclosure of which is incorporated hereinby reference in its entirety. Applicants also contemplate the use ofdiboron, or bis-boron, compounds or other bifunctional compoundscontaining two or more boron atoms in the chemical structure, such asdisclosed in J. Am. Chem. Soc., 2005, 127, pp. 14756-14768, the contentof which is incorporated herein by reference in its entirety.

Generally, any amount of organoboron compound can be used. According toone aspect of this invention, the molar ratio of the total moles oforganoboron or organoborate compound (or compounds) to the total molesof dinuclear metallocene compound (or compounds, including metallocenecompounds) in the catalyst composition is in a range from about 0.1:1 toabout 15:1. Typically, the amount of the fluoroorgano boron orfluoroorgano borate compound used is from about 0.5 moles to about 10moles of boron/borate compound per mole of metallocene compound orcompounds (dinuclear metallocene and any other metallocene, ifapplicable). According to another aspect of this invention, the amountof fluoroorgano boron or fluoroorgano borate compound is from about 0.8moles to about 5 moles of boron/borate compound per mole of metallocenecompound(s).

Ionizing Ionic Compounds

The present invention further provides a catalyst composition comprisingan ionizing ionic compound. An ionizing ionic compound is an ioniccompound that can function as a co-catalyst to enhance the activity ofthe catalyst composition. While not intending to be bound by theory, itis believed that the ionizing ionic compound is capable of reacting witha metallocene compound and converting the metallocene into one or morecationic metallocene compounds, or incipient cationic metallocenecompounds. Again, while not intending to be bound by theory, it isbelieved that the ionizing ionic compound can function as an ionizingcompound by completely or partially extracting an anionic ligand,possibly a non-alkadienyl ligand, from the metallocene. However, theionizing ionic compound is an activator regardless of whether it isionizes the dinuclear metallocene, abstracts a ligand in a fashion as toform an ion pair, weakens the metal-ligand bond in the dinuclearmetallocene, simply coordinates to a ligand, or activates themetallocene by some other mechanism.

Further, it is not necessary that the ionizing ionic compound activatethe metallocene compound(s) only. The activation function of theionizing ionic compound can be evident in the enhanced activity ofcatalyst composition as a whole, as compared to a catalyst compositionthat does not contain an ionizing ionic compound.

Examples of ionizing ionic compounds include, but are not limited to,the following compounds: tri(n-butyl)ammonium tetrakis(p-tolyl)borate,tri(n-butyl)ammonium tetrakis(m-tolyl)borate, tri(n-butyl)ammoniumtetrakis(2,4-dimethylphenyl)borate, tri(n-butyl)ammoniumtetrakis(3,5-dimethylphenyl)borate, tri(n-butyl)ammoniumtetrakis[3,5-bis(trifluoromethyl)phenyl]borate, tri(n-butyl)ammoniumtetrakis(pentafluorophenyl)borate, N,N-dimethylaniliniumtetrakis(p-tolyl)borate, N,N-dimethylanilinium tetrakis(m-tolyl)borate,N,N-dimethylanilinium tetrakis(2,4-dimethylphenyl)borate,N,N-dimethylanilinium tetrakis(3,5-dimethylphenyl)borate,N,N-dimethylanilinium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate,N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate,triphenylcarbenium tetrakis(p-tolyl)borate, triphenylcarbeniumtetrakis(m-tolyl)borate, triphenylcarbeniumtetrakis(2,4-dimethylphenyl)borate, triphenylcarbeniumtetrakis(3,5-dimethylphenyl)borate, triphenylcarbeniumtetrakis[3,5-bis(trifluoromethyl)phenyl]borate, triphenylcarbeniumtetrakis(pentafluorophenyl)borate, tropylium tetrakis(p-tolyl)borate,tropylium tetrakis(m-tolyl)borate, tropyliumtetrakis(2,4-dimethylphenyl)borate, tropyliumtetrakis(3,5-dimethylphenyl)borate, tropylium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate, tropyliumtetrakis(pentafluorophenyl)borate, lithiumtetrakis(pentafluorophenyl)borate, lithium tetraphenylborate, lithiumtetrakis(p-tolyl)borate, lithium tetrakis(m-tolyl)borate, lithiumtetrakis(2,4-dimethylphenyl)borate, lithium tetrakis(3,5-dimethylphenyl)borate, lithium tetrafluoroborate, sodiumtetrakis(pentafluorophenyl)borate, sodium tetraphenylborate, sodiumtetrakis(p-tolyl)borate, sodium tetrakis(m-tolyl)borate, sodium tetrakis(2,4-dimethylphenyl)borate, sodium tetrakis(3,5-dimethylphenyl)borate,sodium tetrafluoroborate, potassium tetrakis-(pentafluorophenyl)borate,potassium tetraphenylborate, potassium tetrakis(p-tolyl)borate,potassium tetrakis(m-tolyl)borate, potassiumtetrakis(2,4-dimethyl-phenyl)borate, potassiumtetrakis(3,5-dimethylphenyl)borate, potassium tetrafluoro-borate,lithium tetrakis(pentafluorophenyl)aluminate, lithiumtetraphenylaluminate, lithium tetrakis(p-tolyl)aluminate, lithiumtetrakis(m-tolyl)aluminate, lithiumtetrakis(2,4-dimethylphenyl)aluminate, lithium tetrakis(3,5-dimethylphenyl)aluminate, lithium tetrafluoroaluminate, sodiumtetrakis(pentafluorophenyl)aluminate, sodium tetraphenylaluminate,sodium tetrakis(p-tolyl)aluminate, sodium tetrakis(m-tolyl)aluminate,sodium tetrakis(2,4-dimethylphenyl)aluminate, sodiumtetrakis(3,5-dimethylphenyl)aluminate, sodium tetrafluoroaluminate,potassium tetrakis(pentafluorophenyl)aluminate, potassiumtetraphenylaluminate, potassium tetrakis(p-tolyl)aluminate, potassiumtetrakis(m-tolyl)aluminate, potassiumtetrakis(2,4-dimethylphenyl)aluminate, potassium tetrakis(3,5-dimethylphenyl)aluminate, potassium tetrafluoroaluminate, and thelike, or combinations thereof. Ionizing ionic compounds useful in thisinvention are not limited to these; other examples of ionizing ioniccompounds are disclosed in U.S. Pat. Nos. 5,576,259 and 5,807,938, thedisclosures of which are incorporated herein by reference in theirentirety.

Olefin Monomers

Unsaturated reactants that can be employed with catalyst compositionsand polymerization processes of this invention typically include olefincompounds having from 2 to 30 carbon atoms per molecule and having atleast one olefinic double bond. This invention encompasseshomopolymerization processes using a single olefin such as ethylene orpropylene, as well as copolymerization, terpolymerization, etc.,reactions using an olefin monomer with at least one different olefiniccompound. For example, the resultant ethylene copolymers, terpolymers,etc., generally contain a major amount of ethylene (>50 mole percent)and a minor amount of comonomer (<50 mole percent), though this is not arequirement. Comonomers that can be copolymerized with ethylene oftenhave from 3 to 20 carbon atoms in their molecular chain.

Acyclic, cyclic, polycyclic, terminal (α), internal, linear, branched,substituted, unsubstituted, functionalized, and non-functionalizedolefins can be employed in this invention. For example, typicalunsaturated compounds that can be polymerized with the catalystcompositions of this invention include, but are not limited to,ethylene, propylene, 1-butene, 2-butene, 3-methyl-1-butene, isobutylene,1-pentene, 2-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1-hexene,2-hexene, 3-hexene, 3-ethyl-1-hexene, 1-heptene, 2-heptene, 3-heptene,the four normal octenes, the four normal nonenes, the five normaldecenes, and the like, or mixtures of two or more of these compounds.Cyclic and bicyclic olefins, including but not limited to, cyclopentene,cyclohexene, norbornylene, norbornadiene, and the like, also can bepolymerized as described above. Styrene can also be employed as amonomer in the present invention.

When a copolymer (or alternatively, a terpolymer) is desired, the olefinmonomer can comprise, for example, ethylene or propylene, which iscopolymerized with at least one comonomer. According to one aspect ofthis invention, the olefin monomer in the polymerization processcomprises ethylene. In this aspect, examples of suitable olefincomonomers include, but are not limited to, propylene, 1-butene,2-butene, 3-methyl-1-butene, isobutylene, 1-pentene, 2-pentene,3-methyl-1-pentene, 4-methyl-1-pentene, 1-hexene, 2-hexene,3-ethyl-1-hexene, 1-heptene, 2-heptene, 3-heptene, 1-octene, 1-decene,styrene, and the like, or combinations thereof. According to one aspectof the present invention, the comonomers comprise 1-butene, 1-pentene,1-hexene, 1-octene, 1-decene, styrene, or any combination thereof.

Generally, the amount of comonomer introduced into a reactor zone toproduce the copolymer is from about 0.01 to about 50 weight percent ofthe comonomer based on the total weight of the monomer and comonomer.According to another aspect of the present invention, the amount ofcomonomer introduced into a reactor zone is from about 0.01 to about 40weight percent comonomer based on the total weight of the monomer andcomonomer. In still another aspect, the amount of comonomer introducedinto a reactor zone is from about 0.1 to about 35 weight percentcomonomer based on the total weight of the monomer and comonomer. Yet,in another aspect, the amount of comonomer introduced into a reactorzone is from about 0.5 to about 20 weight percent comonomer based on thetotal weight of the monomer and comonomer.

While not intending to be bound by this theory, where branched,substituted, or functionalized olefins are used as reactants, it isbelieved that a steric hindrance can impede and/or slow thepolymerization process. Thus, branched and/or cyclic portion(s) of theolefin removed somewhat from the carbon-carbon double bond would not beexpected to hinder the reaction in the way that the same olefinsubstituents situated more proximate to the carbon-carbon double bondmight. According to one aspect of the present invention, at least onemonomer/reactant is ethylene, so the polymerizations are either ahomopolymerization involving only ethylene, or copolymerizations with adifferent acyclic, cyclic, terminal, internal, linear, branched,substituted, or unsubstituted olefin. In addition, the catalystcompositions of this invention can be used in the polymerization ofdiolefin compounds including, but not limited to, 1,3-butadiene,isoprene, 1,4-pentadiene, and 1,5-hexadiene.

Preparation of the Catalyst Composition

In one aspect, the present invention encompasses a catalyst compositioncomprising a contact product of a dinuclear metallocene compound and anactivator-support. Such a composition can further comprise anorganoaluminum compound. Additionally, this catalyst composition canfurther comprise an optional co-catalyst,

wherein the optional co-catalyst is an aluminoxane compound, anorganoboron or organoborate compound, an ionizing ionic compound, or anycombination thereof. In another aspect, a catalyst composition isprovided which comprises the contact product of a dinuclear metallocenecompound and an aluminoxane compound, an organoboron or organoboratecompound, an ionizing ionic compound, or any combination thereof.

This invention further encompasses methods of making these catalystcompositions, such as, for example, contacting the respective catalystcomponents in any order or sequence.

The dinuclear metallocene compound can be precontacted with an olefinicmonomer if desired, not necessarily the olefin monomer to bepolymerized, and an organoaluminum compound for a first period of timeprior to contacting this precontacted mixture with an activator-support.The first period of time for contact, the precontact time, between themetallocene compound or compounds, the olefinic monomer, and theorganoaluminum compound typically ranges from a time period of about0.05 hour to about 24 hours, for example, from about 0.05 hours to about1 hour. Precontact times from about 10 minutes to about 30 minutes arealso employed.

Alternatively, the precontacting process is carried out in multiplesteps, rather than a single step, in which multiple mixtures areprepared, each comprising a different set of catalyst components. Forexample, at least two catalyst components are contacted forming a firstmixture, followed by contacting the first mixture with at least oneother catalyst component forming a second mixture, and so forth.

Multiple precontacting steps can be carried out in a single vessel or inmultiple vessels. Further, multiple precontacting steps can be carriedout in series (sequentially), in parallel, or a combination thereof. Forexample, a first mixture of two catalyst components can be formed in afirst vessel, a second mixture comprising the first mixture plus oneadditional catalyst component can be formed in the first vessel or in asecond vessel, which is typically placed downstream of the first vessel.

In another aspect, one or more of the catalyst components can be splitand used in different precontacting treatments. For example, part of acatalyst component is fed into a first precontacting vessel forprecontacting with at least one other catalyst component, while theremainder of that same catalyst component is fed into a secondprecontacting vessel for precontacting with at least one other catalystcomponent, or is fed directly into the reactor, or a combinationthereof. The precontacting can be carried out in any suitable equipment,such as tanks, stirred mix tanks, various static mixing devices, aflask, a vessel of any type, or combinations of these apparatus.

In another aspect of this invention, the various catalyst components(for example, dinuclear metallocene, activator-support, organoaluminumco-catalyst, and optionally an unsaturated hydrocarbon) are contacted inthe polymerization reactor simultaneously while the polymerizationreaction is proceeding. Alternatively, any two or more of these catalystcomponents can be precontacted in a vessel prior to entering thereaction zone. This precontacting step can be continuous, in which theprecontacted product is fed continuously to the reactor, or it can be astepwise or batchwise process in which a batch of precontacted productis added to make a catalyst composition. This precontacting step can becarried out over a time period that can range from a few seconds to asmuch as several days, or longer. In this aspect, the continuousprecontacting step generally lasts from about 1 second to about 1 hour.In another aspect, the continuous precontacting step lasts from about 10seconds to about 45 minutes, or from about 1 minute to about 30 minutes.

Once the precontacted mixture of the dinuclear metallocene compound,olefin monomer, and organoaluminum co-catalyst is contacted with theactivator-support, this composition (with the addition of theactivator-support) is termed the “postcontacted mixture.” Thepostcontacted mixture optionally remains in contact for a second periodof time, the postcontact time, prior to initiating the polymerizationprocess. Postcontact times between the precontacted mixture and theactivator-support generally range from about 0.05 hours to about 24hours. In a further aspect, the postcontact time is in a range fromabout 0.05 hours to about 1 hour. The precontacting step, thepostcontacting step, or both, can increase the productivity of thepolymer as compared to the same catalyst composition that is preparedwithout precontacting or postcontacting. However, neither aprecontacting step nor a postcontacting step is required.

The postcontacted mixture can be heated at a temperature and for a timeperiod sufficient to allow adsorption, impregnation, or interaction ofprecontacted mixture and the activator-support, such that a portion ofthe components of the precontacted mixture is immobilized, adsorbed, ordeposited thereon. Where heating is employed, the postcontacted mixturegenerally is heated to a temperature of from between about 0° F. toabout 150° F., or from about 40° F. to about 95° F.

According to one aspect of this invention, the molar ratio of the molesof dinuclear metallocene compound to the moles of organoaluminumcompound in a catalyst composition generally is in a range from about1:1 to about 1:10,000. In another aspect, the molar ratio is in a rangefrom about 1:1 to about 1:1,000. Yet, in another aspect, the molar ratioof the moles of dinuclear metallocene compound to the moles oforganoaluminum compound is in a range from about 1:1 to about 1:100.These molar ratios reflect the ratio of total moles of dinuclearmetallocene compound (or compounds, including additional metallocene ordinuclear metallocene) to the total amount of organoaluminum compound(or compounds) in both the precontacted mixture and the postcontactedmixture combined, if precontacting and/or postcontacting steps areemployed.

When a precontacting step is used, the molar ratio of the total moles ofolefin monomer to total moles of dinuclear metallocene in theprecontacted mixture is typically in a range from about 1:10 to about100,000:1. Total moles of each component are used in this ratio toaccount for aspects of this invention where more than one olefin monomerand/or more than metallocene and/or dinuclear metallocene is employed.Further, this molar ratio can be in a range from about 10:1 to about1,000:1 in another aspect of the invention.

Generally, the weight ratio of organoaluminum compound toactivator-support is in a range from about 10:1 to about 1:1000. If morethan one organoaluminum compound and/or more than one activator-supportis employed, this ratio is based on the total weight of each respectivecomponent. In another aspect, the weight ratio of the organoaluminumcompound to the activator-support is in a range from about 3:1 to about1:100, or from about 1:1 to about 1:50.

In some aspects of this invention, the weight ratio of dinuclearmetallocene to activator-support is in a range from about 1:1 to about1:1,000,000. If more than one dinuclear metallocene (or additionalmetallocene compound or compounds) and/or more than oneactivator-support is employed, this ratio is based on the total weightof each respective component. In another aspect, this weight ratio is ina range from about 1:5 to about 1:100,000, or from about 1:10 to about1:10,000. Yet, in another aspect, the weight ratio of the metallocenecompound(s) to the activator-support is in a range from about 1:20 toabout 1:1000.

According to some aspects of this invention, aluminoxane compounds arenot required to form the catalyst composition. Thus, the polymerizationproceeds in the absence of aluminoxanes. Accordingly, the presentinvention can use, for example, organoaluminum compounds and anactivator-support in the absence of aluminoxanes. While not intending tobe bound by theory, it is believed that the organoaluminum compoundlikely does not activate the metallocene catalyst in the same manner asan organoaluminoxane compound.

Additionally, in some aspects, organoboron and organoborate compoundsare not required to form a catalyst composition of this invention.Nonetheless, aluminoxanes, organoboron or organoborate compounds,ionizing ionic compounds, or combinations thereof can be used in othercatalyst compositions contemplated by and encompassed within the presentinvention. Hence, aluminoxanes, organoboron or organoborate compounds,ionizing ionic compounds, or combinations thereof, can be employed withthe dinuclear metallocene compound, either in the presence or in theabsence of an activator-support, and either in the presence or in theabsence of an organoaluminum compound.

Catalyst compositions of the present invention generally have a catalystactivity greater than about 100 grams of polyethylene (homopolymer,copolymer, etc., as the context requires) per gram of activator-supportper hour (abbreviated gP/(gAS·hr)). In another aspect, the catalystactivity is greater than about 150, greater than about 200, or greaterthan about 250 gP/(gAS·hr). In still another aspect, catalystcompositions of this invention are characterized by having a catalystactivity greater than about 500, greater than about 1000, or greaterthan about 1500 gP/(gAS·hr). Yet, in another aspect, the catalystactivity is greater than about 2000 gP/(gAS·hr). This activity ismeasured under slurry polymerization conditions using isobutane as thediluent, at a polymerization temperature of about 90° C. and an ethylenepressure of about 550 psig.

Other aspects of the present invention do not require anactivator-support. These catalyst compositions comprise a contactproduct of a dinuclear metallocene compound and an aluminoxane compound,an organoboron or organoborate compound, an ionizing ionic compound, orany combination thereof. Such catalyst compositions of the presentinvention generally have catalyst activities greater than about 100grams of polyethylene per hour per gram of the respective aluminoxanecompound, organoboron or organoborate compound, ionizing ionic compound,or combination thereof. In another aspect, the catalyst activity isgreater than about 250, or greater than about 500 grams of polyethyleneper hour per gram of the respective aluminoxane compound, organoboron ororganoborate compound, ionizing ionic compound, or combination thereof.Yet, in another aspect, the catalyst activity is greater than about1000, or greater than about 2000 grams of polyethylene per hour.

As discussed above, any combination of the dinuclear metallocenecompound, the activator-support, the organoaluminum compound, and theolefin monomer, can be precontacted in some aspects of this invention.When any precontacting occurs with an olefinic monomer, it is notnecessary that the olefin monomer used in the precontacting step be thesame as the olefin to be polymerized. Further, when a precontacting stepamong any combination of the catalyst components is employed for a firstperiod of time, this precontacted mixture can be used in a subsequentpostcontacting step between any other combination of catalyst componentsfor a second period of time. For example, the dinuclear metallocenecompound, the organoaluminum compound, and 1-hexene can be used in aprecontacting step for a first period of time, and this precontactedmixture then can be contacted with the activator-support to form apostcontacted mixture that is contacted for a second period of timeprior to initiating the polymerization reaction. For example, the firstperiod of time for contact, the precontact time, between any combinationof the metallocene compound, the olefinic monomer, theactivator-support, and the organoaluminum compound can be from about0.05 hours to about 24 hours, from about 0.05 hours to about 1 hour, orfrom about 10 minutes to about 30 minutes. The postcontacted mixtureoptionally is allowed to remain in contact for a second period of time,the postcontact time, prior to initiating the polymerization process.According to one aspect of this invention, postcontact times between theprecontacted mixture and any remaining catalyst components is from about0.05 hours to about 24 hours, or from about 0.1 hour to about 1 hour.

Polymerization Process

Catalyst compositions of the present invention can be used to polymerizeolefins to form homopolymers, copolymers, terpolymers, and the like. Onesuch process for polymerizing olefins in the presence of a catalystcomposition of the present invention comprises contacting the catalystcomposition with an olefin monomer and optionally an olefin comonomerunder polymerization conditions to produce an olefin polymer, whereinthe catalyst composition comprises a contact product of a dinuclearmetallocene compound and an activator-support. The dinuclear metallocenecompound in the catalyst compositions can have any of the formulas (A),(B), (C), (IA)=(IB), (IIA)=(IIB), or (IIIA)=(IIIB) discussed above.

Often, a catalyst composition of the present invention, employed in apolymerization process, will further comprise an organoaluminumcompound. Suitable organoaluminum compounds include, but are notlimited, to trimethylaluminum (TMA), triethylaluminum (TEA),tri-n-propylaluminum (TNPA), tri-n-butylaluminum (TNBA),triisobutylaluminum (TIBA), tri-n-hexylaluminum, tri-n-octylaluminum,diisobutylaluminum hydride, diethylaluminum ethoxide, diethylaluminumchloride, and the like, or combinations thereof.

The catalyst compositions of the present invention are intended for anyolefin polymerization method using various types of polymerizationreactors. As used herein, “polymerization reactor” includes anypolymerization reactor capable of polymerizing olefin monomers andcomonomers (one or more than one comonomer) to produce homopolymers,copolymers, terpolymers, and the like. The various types of reactorsinclude those that may be referred to as batch, slurry, gas-phase,solution, high pressure, tubular, or autoclave reactors. Gas phasereactors may comprise fluidized bed reactors or staged horizontalreactors. Slurry reactors may comprise vertical or horizontal loops.High pressure reactors may comprise autoclave or tubular reactors.Reactor types can include batch or continuous processes. Continuousprocesses could use intermittent or continuous product discharge.Processes may also include partial or full direct recycle of unreactedmonomer, unreacted comonomer, and/or diluent.

Polymerization reactor systems of the present invention may comprise onetype of reactor in a system or multiple reactors of the same ordifferent type. Production of polymers in multiple reactors may includeseveral stages in at least two separate polymerization reactorsinterconnected by a transfer device making it possible to transfer thepolymers resulting from the first polymerization reactor into the secondreactor. The desired polymerization conditions in one of the reactorsmay be different from the operating conditions of the other reactors.Alternatively, polymerization in multiple reactors may include themanual transfer of polymer from one reactor to subsequent reactors forcontinued polymerization. Multiple reactor systems may include anycombination including, but not limited to, multiple loop reactors,multiple gas phase reactors, a combination of loop and gas phasereactors, multiple high pressure reactors, or a combination of highpressure with loop and/or gas phase reactors. The multiple reactors maybe operated in series or in parallel.

According to one aspect of the invention, the polymerization reactorsystem may comprise at least one loop slurry reactor comprising verticalor horizontal loops. Monomer, diluent, catalyst, and comonomer may becontinuously fed to a loop reactor where polymerization occurs.Generally, continuous processes may comprise the continuous introductionof monomer/comonomer, a catalyst, and a diluent into a polymerizationreactor and the continuous removal from this reactor of a suspensioncomprising polymer particles and the diluent. Reactor effluent may beflashed to remove the solid polymer from the liquids that comprise thediluent, monomer and/or comonomer. Various technologies may be used forthis separation step including but not limited to, flashing that mayinclude any combination of heat addition and pressure reduction;separation by cyclonic action in either a cyclone or hydrocyclone; orseparation by centrifugation.

A typical slurry polymerization process (also known as the particle formprocess) is disclosed, for example, in U.S. Pat. Nos. 3,248,179,4,501,885, 5,565,175, 5,575,979, 6,239,235, 6,262,191, and 6,833,415,each of which is incorporated herein by reference in its entirety.

Suitable diluents used in slurry polymerization include, but are notlimited to, the monomer being polymerized and hydrocarbons that areliquids under reaction conditions. Examples of suitable diluentsinclude, but are not limited to, hydrocarbons such as propane,cyclohexane, isobutane, n-butane, n-pentane, isopentane, neopentane, andn-hexane. Some loop polymerization reactions can occur under bulkconditions where no diluent is used. An example is polymerization ofpropylene monomer as disclosed in U.S. Pat. No. 5,455,314, which isincorporated by reference herein in its entirety.

According to yet another aspect of this invention, the polymerizationreactor may comprise at least one gas phase reactor. Such systems mayemploy a continuous recycle stream containing one or more monomerscontinuously cycled through a fluidized bed in the presence of thecatalyst under polymerization conditions. A recycle stream may bewithdrawn from the fluidized bed and recycled back into the reactor.Simultaneously, polymer product may be withdrawn from the reactor andnew or fresh monomer may be added to replace the polymerized monomer.Such gas phase reactors may comprise a process for multi-step gas-phasepolymerization of olefins, in which olefins are polymerized in thegaseous phase in at least two independent gas-phase polymerization zoneswhile feeding a catalyst-containing polymer formed in a firstpolymerization zone to a second polymerization zone. One type of gasphase reactor is disclosed in U.S. Pat. Nos. 5,352,749, 4,588,790, and5,436,304, each of which is incorporated by reference in its entiretyherein.

According to still another aspect of the invention, a high pressurepolymerization reactor may comprise a tubular reactor or an autoclavereactor. Tubular reactors may have several zones where fresh monomer,initiators, or catalysts are added. Monomer may be entrained in an inertgaseous stream and introduced at one zone of the reactor. Initiators,catalysts, and/or catalyst components may be entrained in a gaseousstream and introduced at another zone of the reactor. The gas streamsmay be intermixed for polymerization. Heat and pressure may be employedappropriately to obtain optimal polymerization reaction conditions.

According to yet another aspect of the invention, the polymerizationreactor may comprise a solution polymerization reactor wherein themonomer/comonomer are contacted with the catalyst composition bysuitable stirring or other means. A carrier comprising an inert organicdiluent or excess monomer may be employed. If desired, themonomer/comonomer may be brought in the vapor phase into contact withthe catalytic reaction product, in the presence or absence of liquidmaterial. The polymerization zone is maintained at temperatures andpressures that will result in the formation of a solution of the polymerin a reaction medium. Agitation may be employed to obtain bettertemperature control and to maintain uniform polymerization mixturesthroughout the polymerization zone. Adequate means are utilized fordissipating the exothermic heat of polymerization.

Polymerization reactors suitable for the present invention may furthercomprise any combination of at least one raw material feed system, atleast one feed system for catalyst or catalyst components, and/or atleast one polymer recovery system. Suitable reactor systems for thepresent invention may further comprise systems for feedstockpurification, catalyst storage and preparation, extrusion, reactorcooling, polymer recovery, fractionation, recycle, storage, loadout,laboratory analysis, and process control.

Conditions that are controlled for polymerization efficiency and toprovide desired polymer properties include temperature, pressure, andthe concentrations of various reactants. Polymerization temperature canaffect catalyst productivity, polymer molecular weight, and molecularweight distribution. Suitable polymerization temperature may be anytemperature below the de-polymerization temperature according to theGibbs Free energy equation. Typically, this includes from about 60° C.to about 280° C., for example, or from about 60° C. to about 110° C.,depending upon the type of polymerization reactor. In some reactorsystems, the polymerization temperature generally is within a range fromabout 70° C. to about 90° C., or from about 75° C. to about 85° C.

Suitable pressures will also vary according to the reactor andpolymerization type. The pressure for liquid phase polymerizations in aloop reactor is typically less than 1000 psig. Pressure for gas phasepolymerization is usually at about 200 to 500 psig. High pressurepolymerization in tubular or autoclave reactors is generally run atabout 20,000 to 75,000 psig. Polymerization reactors can also beoperated in a supercritical region occurring at generally highertemperatures and pressures. Operation above the critical point of apressure/temperature diagram (supercritical phase) may offer advantages.

According to one aspect of this invention, the ratio of hydrogen to theolefin monomer in the polymerization process is controlled. This weightratio can range from 0 ppm to about 10,000 ppm of hydrogen, based on theweight of the olefin monomer. For instance, the reactant or feed ratioof hydrogen to olefin monomer can be controlled at a weight ratio whichfalls within a range from about 25 ppm to about 7500 ppm, from about 50ppm to about 5000 ppm, or from about 50 ppm to about 1000 ppm.

In ethylene polymerizations, the feed ratio of hydrogen to ethylenemonomer, irrespective of comonomer(s) employed, generally is controlledat a weight ratio within a range from about 0 ppm to about 1000 ppm, butthe specific weight ratio target can depend upon the desired polymermolecular weight or melt index (MI). For ethylene polymers(homopolymers, copolymers, etc.) having a MI around 1 g/10 min, theweight ratio of hydrogen to ethylene is typically in a range from about25 ppm to about 250 ppm, such as, for example, from about 50 ppm toabout 225 ppm, or from about 75 ppm to about 200 ppm.

Yet, in another aspect, effluent flush gas from the polymerizationreactors disclosed herein generally has a hydrogen to olefin monomermolar ratio of less than about 0.01, although this ratio can depend uponthe desired polymer molecular weight, MI, etc. In an ethylenepolymerization, the hydrogen:ethylene molar ratio typically can be lessthan about 0.01, and often, less than about 0.005.

The concentration of the reactants entering the polymerization reactorcan be controlled to produce resins with certain physical and mechanicalproperties. The proposed end-use product that will be formed by thepolymer resin and the method of forming that product ultimately candetermine the desired polymer properties and attributes. Mechanicalproperties include tensile, flexural, impact, creep, stress relaxation,and hardness tests. Physical properties include density, molecularweight, molecular weight distribution, melting temperature, glasstransition temperature, temperature melt of crystallization, density,stereoregularity, crack growth, long chain branching, and rheologicalmeasurements.

This invention is also directed to the polymers produced by any of thepolymerization processes disclosed herein. Articles of manufacture canbe formed from, and can comprise, the polymers produced in accordancewith this invention.

Polymers and Articles

If the resultant polymer produced in accordance with the presentinvention is, for example, a polymer or copolymer of ethylene, itsproperties can be characterized by various analytical techniques knownand used in the polyolefin industry. Articles of manufacture can beformed from, and can comprise, the ethylene polymers of this invention,whose typical properties are provided below.

Polymers of ethylene (homopolymers, copolymers, terpolymers, etc.)produced in accordance with this invention generally have a melt indexfrom about 0.01 to about 100 g/10 min. Melt indices in the range fromabout 0.1 to about 50 g/10 min, or from about 0.5 to about 25 g/10 min,are contemplated in some aspects of this invention.

The density of ethylene-based polymers produced using one or moredinuclear metallocene compounds disclosed herein typically falls withinthe range from about 0.88 to about 0.97 g/cm³. In one aspect of thisinvention, the density of an ethylene polymer is in a range from about0.90 to about 0.95 g/cm³. Yet, in another aspect, the density is in arange from about 0.91 to about 0.94 g/cm³.

Polymers of ethylene, whether homopolymers, copolymers, terpolymers, andso forth, can be formed into various articles of manufacture. Articleswhich can comprise polymers of this invention include, but are notlimited to, an agricultural film, an automobile part, a bottle, a drum,a fiber or fabric, a food packaging film or container, a food servicearticle, a fuel tank, a geomembrane, a household container, a liner, amolded product, a medical device or material, a pipe, a sheet or tape, atoy, and the like. Various processes can be employed to form thesearticles. Non-limiting examples of these processes include injectionmolding, blow molding, rotational molding, film extrusion, sheetextrusion, profile extrusion, thermoforming, and the like. Additionally,additives and modifiers are often added to these polymers in order toprovide beneficial polymer processing or end-use product attributes.

EXAMPLES

The invention is further illustrated by the following examples, whichare not to be construed in any way as imposing limitations to the scopeof this invention. Various other aspects, embodiments, modifications,and equivalents thereof which, after reading the description herein, maysuggest themselves to one of ordinary skill in the art without departingfrom the spirit of the present invention or the scope of the appendedclaims.

Nuclear Magnetic Resonance (NMR) spectra were obtained on a VarianMercury Plus 300 NMR spectrometer operating at 300 MHz for ¹H NMR (CDCl₃solvent, referenced against the peak of residual CHCl₃ at 7.24 ppm) and75 MHz for ¹³C NMR (CDCl₃ solvent, referenced against central line ofCHCl₃ at 77.00 ppm).

In addition to NMR, a thermal desorption mass spectrometry procedure(direct insertion probe mass spectrometry or DIPMS) was used tocharacterize and identify the dinuclear metallocene compounds in theexamples. The mass spectrometer had the following capabilities: 70 evelectron impact ionization, mass range from 35 to 1200 amu, direct probeinsertion accessory with maximum temperature to at least 650° C., andsoftware capable of integrating broad peaks typical of probe runs. Themethod was developed using a Finnigan™ TSQ 7000™ instrument, scan rangeof 35 to 1400 (1 second scan time), conventional thin wire (with loop attip) probe tips, source temperature of 180° C., 2×10-6 manifold vacuum,and Finnigan™ Excalibur™ software for peak integration and instrumentcontrol. Other instruments having comparable mass range and probecapabilities could be utilized.

In the DIPMS procedure, the sample is placed on the probe tip using amicro syringe. In practice, the smallest drop of sample which can betransferred to the probe usually gives the best results. After placingthe sample on the probe, it is allowed to stand for about 5-10 min toallow for evaporation of the bulk of the diluent/solvent containing thecompound of interest. Allowing the diluent/solvent to evaporate beforeinserting the probe into the instrument will, among other things, lessenthe chance that the drop will fall off of the tip during the insertionprocess. After inserting the probe, the temperature program and dataacquisition cycles begin. The temperature program used was 50° C. (hold1 min), 30° C./min temperature ramp, 650° C. final temperature (hold 5min) This program takes 26 minutes to complete. The filament was turnedon 0.5 min into the run and kept on until the completion of thetemperature program. After a couple of minutes to allow the probe tip tocool, the probe was removed from the instrument and the analysis cyclewas complete.

The Finnigan™ instrument had removable ion volumes; these were changedand cleaned after every two runs to minimize buildup of residue on thelens and other source components. The results are typically outputted asplots showing total ion current versus time.

Melt index (MI, g/10 min) was determined in accordance with ASTM D1238at 190° C. with a 2,160 gram weight.

High load melt index (HLMI, g/10 min) was determined in accordance withASTM D1238 at 190° C. with a 21,600 gram weight.

Polymer density was determined in grams per cubic centimeter (g/cc) on acompression molded sample, cooled at about 15° C. per hour, andconditioned for about 40 hours at room temperature in accordance withASTM D1505 and ASTM D1928, procedure C.

Melt rheological characterizations were determined by suitable methods.For example, small-strain (10%) oscillatory shear measurements wereperformed on a Rheometrics Scientific, Inc. ARES rheometer usingparallel-plate geometry. All rheological tests were performed at 190° C.

Molecular weights and molecular weight distributions were obtained usinga PL 220 SEC high temperature chromatography unit (Polymer Laboratories)with trichlorobenzene (TCB) as the solvent, with a flow rate of 1mL/minute at a temperature of 145° C. BHT(2,6-di-tert-butyl-4-methylphenol) at a concentration of 0.5 g/L wasused as a stabilizer in the TCB. An injection volume of 200 μL was usedwith a nominal polymer concentration of 1.5 mg/mL. Dissolution of thesample in stabilized TCB was carried out by heating at 150° C. for 5hours with occasional, gentle agitation. The columns used were threePLgel Mixed A LS columns (7.8×300 mm) and were calibrated with a broadlinear polyethylene standard (Phillips Marlex® BHB 5003) for which themolecular weight had been determined

Molecular weight distributions and branch profiles were obtained throughsize exclusion chromatography (SEC) using an FTIR detector.Chromatographic conditions are those described above. However, thesample injection volume was 500 μL. Samples were introduced to the FTIRdetector via a heated transfer line and flow cell (KBr windows, 1 mmoptical path, and ca. 70 μL cell volume). The temperatures of thetransfer line and flow cell were kept at 143±1° C. and 140±1° C.,respectively. A Perkin Elmer FTIR spectrophotometer (PE 2000) equippedwith a narrow band mercury cadmium telluride (MCT) detector was used inthese studies.

All spectra were acquired using Perkin Elmer Timebase software.Background spectra of the TCB solvent were obtained prior to each run.All IR spectra were measured at 8 cm⁻¹ resolution (16 scans).Chromatograms were generated using the root mean square absorbance overthe 3000-2700 cm⁻¹ spectral region (i.e., FTIR serves as a concentrationdetector). Molecular weight calculations were made as previouslydescribed using a broad molecular weight polyethylene (PE) standard [seeJordens K, Wilkes G L, Janzen J, Rohlfing D C, Welch M B, Polymer 2000;41:7175]. Spectra from individual time slices of the chromatogram weresubsequently analyzed for comonomer branch levels using chemometrictechniques. All calibration spectra were taken at sample concentrationswhich far exceeded that needed for good signal to noise (i.e., >0.08mg/mL at the detector).

Sulfated alumina was formed by a process wherein alumina waschemically-treated with a sulfate or bisulfate source. Such a sulfate orbisulfate source may include, for example, sulfuric acid, ammoniumsulfate, or ammonium bisulfate. In an exemplary procedure, a commercialalumina sold as W.R. Grace Alumina A was sulfated by impregnation withan aqueous solution containing about 15-20% (NH₄)₂SO₄ or H₂SO₄. Thissulfated alumina was calcined at 550° C. in air (240° C./hr ramp rate),with a 3 hr hold period at this temperature. Afterward, the sulfatedalumina was collected and stored under dry nitrogen, and was usedwithout exposure to the atmosphere.

Example 1 Synthesis of DMET-1 using olefin metathesis ofdiphenylmethylidene(3-(penten-4-yl)cyclopentadienyl)(9-2,7-di-tert-butylfluorenyl)hafniumdichloride with (n-butylcyclopentadienyl)(1-allylindenyl)zirconiumdichloride

DMET-1 is a nano-linked, heterodinuclear compound of the presentedinvention. It was produced using two different metallocene reactants andis, therefore, a heteronuclear compound. The first reactant metalloceneused to produce DMET-1 was diphenylmethylidene(3-(penten-4-yl)cyclopentadienyl) (9-2,7-di-tert-butylfluorenyl) hafniumdichloride (abbreviated “MET-1”). The second reactant metallocene usedwas (n-butylcyclopentadienyl)(1-allylindenyl) zirconium dichloride, or{C₅H₄—[(CH₂)₃CH₃] (C₉H₆-l-(CH₂CH═CH₂)}ZrCl₂, C₂₁H₂₄ZrCl₂ (abbreviated“MET-2”). The reaction scheme for this inventive example is illustratedbelow (Ph=Phenyl):

The MET-1 and MET-2 metallocene starting materials can be prepared inaccordance with suitable methods. Illustrative techniques are describedin U.S. Pat. Nos. 7,517,939 and 7,226,886, the disclosures of which areincorporated herein by reference in their entirety.

Approximately 3.3 g (4 mmol, 824.23 g/mol) of MET-1 and 1.75 g (4 mmol,438.54 g/mol) of MET-2 were charged to a reactor under an inert nitrogenatmosphere. About 100 mL of toluene were added to the reactor, forming adark brown solution. The resultant solution was decanted into a reactorcontaining approximately 100 mg ofbis(tricyclohexylphosphine)benzylidine ruthenium (IV) dichloride (Grubbsfirst generation metathesis catalyst). The reactor contents were stirredfor 14 days under an inert atmosphere, and the ethylene produced wasvented. The resultant reaction mixture was subsequently allowed tosettle.

The solution from the reaction mixture was decanted from the settledsolids and then stripped under a high vacuum creating a brown solidresidue (solid product denoted as catalyst fraction B). The brown solidresidue was treated with a mixture containing 40 mL of pentane and 4 mLof toluene. The resultant mixture was again decanted and the solvent wascollected (solid product denoted as catalyst fraction A). The solublefraction was stripped and then treated successively with 40 mL ofpentane and 4 mL of toluene (solid product denoted as catalyst fractionC). This solubility-based separation process was repeated a total ofthree times. The solid product of fraction B was about 1.033 g of abrown solid, the solid product of fraction A was about 0.812 g of ayellow to light brown solid, and the solid product of fraction C wasabout 1.286 g of a yellow solid. The final soluble fraction wasconcentrated to a yellow-brown solid (denoted as catalyst fraction D)weighing about 1.9 g. These catalyst fractions were evaluated inpolymerization reactions, see Examples 3-16.

A sample of each catalyst fraction was dissolved in D-chloroform to forma solution for analysis by ¹H-NMR. FIGS. 1-4 present NMR data forcatalyst fractions A-D, respectively. FIGS. 5-6 present NMR data for thehomodinuclear compounds based on MET-2 and MET-1, respectively. Thedistinct NMR resonances present in FIGS. 1-4—that are not related toeither homodinuclear compounds (I.e., as in FIGS. 5-6), metallocenereactants, or to solvents—indicate the presence of the desiredheterodinuclear compound, DMET-1.

Example 2 Synthesis of DMET-1 and Subsequent Hydrolysis of DMET-1 to theFree Ligand, C₅₄H₅₆

Approximately 76 mg of MET-1, 40 mg of MET-2, and 2 mg ofbis(tricyclohexylphosphine)benzylidine ruthenium (IV) dichloride (Grubbsfirst generation metathesis catalyst) were charged to a vial anddissolved in 2 mL of benzene-d6. After 3 days, a sample of the reactionmixture was hydrolyzed with a mixture containing about 30 microliters ofwater in about 0.5 mL of toluene. As shown in the following reactionscheme, the metal was hydrolyzed to the free ligand (C₅₄H₅₆) and theligand was subsequently characterized.

The free ligand (C₅₄H₅₆) sample was analyzed using the thermaldesorption mass spectrometry procedure, DIPMS, outlined above. Asillustrated in FIGS. 7-8, the prominent molecular ion observed wasconsistent with the expected molecular mass of 704 Daltons of the freeligand (C₅₄H₅₆), indicating that the DMET-1 was produced.

Examples 3-16 Polymerization Runs Using Catalyst Systems ContainingDMET-1

Dinuclear metallocene compounds of the present invention were used aspart of a catalyst system to polymerize olefins. All polymerizationswere conducted in a one-gallon stainless steel semi-batch reactor.Isobutane and alkyl aluminum co-catalyst were used in all polymerizationexperiments. The typical polymerization procedure was conducted asfollows: alkyl aluminum, the activator-support and the metallocene wereadded in order through a charge port while venting isobutane vapor. Thecharge port was closed and about 2 liters of isobutane were added. Thecontents of the reactor were stirred and heated to the desired runtemperature, and ethylene was then introduced along with the desiredamount of hexene. Ethylene was fed on demand to maintain the specifiedpressure for the specified length of the polymerization run. The reactorwas maintained and controlled at the desired run temperature throughoutthe polymerization. Upon completion, the ethylene flow was stopped andthe reactor pressure slowly vented off. The reactor was opened and thepolymer product was collected and dried under vacuum at approximately50° C. for at least two hours.

Table I summarizes the catalyst system formulations employed forExamples 3-16. In Examples 3-16, the catalyst fractions of Example 1were evaluated. These catalyst fractions contained DMET-1, thehomodinuclear compound based on MET-1, and the homodinuclear compoundbased on MET-2 (and small amounts of unreacted metallocenes MET-1 andMET-2). The specific polymerization conditions were a 30 minute runtime, reaction temperature of 80° C. or 95° C., 450 psig ethylene feed,45 grams of 1-hexene, and 0.5 mmol of triisobutylaluminum (TIBA) per 100mg of sulfated alumina. The loading of the catalyst fraction was variedin Examples 3-16.

TABLE I Examples 3-16 using catalyst fractions from Example 1. Catalystmg Temp Example Fraction Catalyst (° C.) mg A-S g PE HLMI 3 C 1 80 10825.2 0.22 4 C 2.5 80 120 19.3 0.01 5 A 1 80 107 39.4 0.97 6 A 1 95 14133.7 1.5 7 A 2.5 95 95 42.5 2.5 8 A 2.5 80 109 44.7 0.74 9 B 1 80 8116.9 0.31 10 B 2.5 80 106 37.2 0.75 11 B 1 95 103 22.6 0.79 12 B 2.5 95105 37.6 1.96 13 D 1 80 98 37.5 1.73 14 D 2.5 80 74 60.9 0.5 15 D 1 9592 35.8 1.1 16 D 2.5 95 113 51.7 1.92 Notes on Table I: mgA-S—milligrams of sulfated alumina activator-support. g PE—gramsethylene/hexene copolymer produced. MI was too low to measure; HLMI inunits of g/10 min.

Table II summarizes molecular weight distribution data for each ofExamples 3-16. This data was generated using size exclusionchromatography, in accordance with the procedure discussed above.

TABLE II Molecular weight distribution data for Examples 3-16 ExampleMn/1000 Mw/1000 Mz/1000 Mw/Mn 3 108.9 707 2876 6.5 4 130.0 761 2657 5.85 102.6 472 2451 4.6 6 56.2 410 2114 7.3 7 43.8 356 1652 8.1 8 97.4 4662267 4.8 9 92.7 602 2669 6.5 10 99.6 531 2553 5.3 11 74.1 424 1719 5.712 63.7 387 1674 6.1 13 115.8 684 2825 5.9 14 99.4 651 2803 6.6 15 63.6430 1589 6.8 16 59.6 433 1566 7.3 Notes on Table II: Mn - number-averagemolecular weight. Mw - weight-average molecular weight. Mz - z-averagemolecular weight. Mw/Mn - PDI or polydispersity index.

Example 17 Synthesis of DMET-2 using olefin metathesis of1-(methyl)-1-(3-butenyl)-1-(cyclopentadienyl)-1-(2,7-di-tert-butylfluoren-1-yl)methanezirconium dichloride with (n-butylcyclopentadienyl)(1-allylindenyl)zirconium dichloride

DMET-2 is a nano-linked, heterodinuclear compound of the presentedinvention. It was produced using two different metallocene reactants andis, therefore, a heteronuclear compound. The first reactant metalloceneused to produce

DMET-2 was1-(methyl)-1-(3-butenyl)-1-(cyclopentadienyl)-1-(2,7-di-tert-butylfluoren-1-yl)methanezirconium dichloride (abbreviated “MET-3”). The second reactantmetallocene used was (n-butylcyclopentadienyl)(1-allylindenyl) zirconiumdichloride, or {C₅H₄—[(CH₂)₃ CH₃] (C₉H₆-l-(CH₂CH═CH₂)}ZrCl₂, C₂₁H₂₄ZrCl₂(abbreviated “MET-2”). The reaction scheme for this inventive example isillustrated below:

The MET-3 metallocene starting material can be prepared in accordancewith suitable methods. One such technique is described in U.S. Pat. No.7,064,225, the disclosure of which is incorporated herein by referencein its entirety.

Approximately 1.28 g (2.2 mmol, 584.77 g/mol) of MET-3 were dissolved in40 mL of toluene and 0.98 (2.2 mmol, 438.54 g/mol) of MET-2 weredissolved in 60 mL of toluene, and these solutions were charged to areactor under an inert nitrogen atmosphere. The resultant solution had aburnt orange color. While stirring, a solution of 0.057 g ofbis(tricyclohexylphosphine)benzylidine ruthenium (IV) dichloride (Grubbsfirst generation metathesis catalyst) in 10 mL of toluene was added tothe reactor. The reactor contents were stirred at room temperature underan inert atmosphere, and the ethylene produced was vented. After about28 hours, approximately 0.052 g of additional metathesis catalyst in 5mL of toluene were added. After 6 total days of reaction, theheterogeneous turbid-reddish reaction mixture was concentrated undervacuum. The residue was successively washed with three 20-mL portions ofpentane. The resultant product was then vacuum dried to a salmon-orangecolored solid, which was used in Examples 18-26 without furtherpurification.

A sample of this product was dissolved in D-chloroform to form asolution for analysis by ¹H-NMR. FIG. 9 presents NMR data for thisproduct mixture. FIG. 10 presents NMR data for the homodinuclearcompound based on MET-3. The distinct NMR resonances present in FIG.9—that are not related to either homodinuclear compounds (i.e., as inFIGS. 5 and 10), metallocene reactants, or to solvents—indicate thepresence of the desired heterodinuclear compound, DMET-2.

Example 18 Hydrolysis of DMET-2 to the Free Ligand

A sample of the reaction product of Example 17 (containing DMET-2) wascharged to a vial and treated with about 0.5 mL of D-chloroform and 5microliters of water. This mixture was allowed to hydrolyze for 2 daysat ambient temperature. As shown in the following reaction scheme, themetal was hydrolyzed to the free ligand and the ligand was subsequentlycharacterized.

The free ligand sample was analyzed using the thermal desorption massspectrometry procedure, DIPMS, outlined above. As illustrated in FIG.11, the prominent molecular ion observed was consistent with theexpected molecular mass of 552 Daltons of the free ligand, indicatingthat the DMET-2 was produced.

Examples 19-26 Polymerization Runs Using Catalyst Systems ContainingDMET-2

Polymerization runs for Examples 19-26 used substantially the sameprocedure as that of Examples 3-16. Table III summarizes the catalystsystem formulations employed for Examples 19-26. In Examples 19-26, thereaction product of Example 17 was evaluated. This product containedDMET-2, the homodinuclear compound based on MET-3, and the homodinuclearcompound based on MET-2 (and small amounts of unreacted MET-2 andMET-3). The specific polymerization conditions were a 30 minute runtime, reaction temperature of 80° C., 420 psig ethylene feed, 45 gramsof 1-hexene, and 0.5 mmol of triisobutylaluminum (TIBA) per 100 mg ofthe activator-support. The loading of the catalyst relative to theactivator-support was varied in Examples 19-26.

TABLE III Examples 19-26 using the catalyst product from Example 17.Example mg catalyst A-S g PE MI HLMI SR 19 2.5 SA 100 0.13 5.52 42.46 204.0 SA 133 0.15 5.91 39.40 21 5.0 SA 149 0.15 6.96 46.40 22 8.0 SA 1760.08 5.34 66.75 23 1.5 FAS 141 0.09 4.32 48.00 24 2.0 FAS 160 0.10 4.4344.30 25 4.0 FAS 124 0.14 6.70 47.85 26 8.0 FAS 83 0.21 7.95 37.86 Noteson Table III: A-S—activator-support used: SA for sulfated alumina; FASfor fluorided silica-alumina, as described in Example 3 (A-S3) in U.S.patent application No. 12/052,620, which is incorporated herein byreference in its entirety. g PE—grams ethylene/hexene copolymerproduced. MI and HLMI - units of g/10 min. SR—shear ratio, HLMI/MI.

1. A dinuclear metallocene compound having the formula:

wherein: each X¹, X², X⁵, X⁶, X⁹, and X¹⁶ independently is hydrogen;BH₄; a halide; a hydrocarbyl group, hydrocarbyloxide group,hydrocarbyloxylate group, hydrocarbylamino group, or hydrocarbylsilylgroup, any of which having up to 20 carbon atoms; or OBR^(A) ₂ orSO₃R^(A), wherein R^(A) is an alkyl group or aryl group having up to 12carbon atoms; each X³ independently is a substituted or unsubstitutedcyclopentadienyl, indenyl, or fluorenyl group, any substituents on X³independently are a hydrogen atom or a substituted or unsubstitutedalkyl or alkenyl group; each X⁴ independently is a substitutedcyclopentadienyl, indenyl, or fluorenyl group, any substituents on X⁴other than an alkenyl linking group independently are a hydrogen atom ora substituted or unsubstituted alkyl or alkenyl group; each X⁷, X¹¹, andX¹² independently is a substituted cyclopentadienyl, indenyl, orfluorenyl group, any substituents on X⁷, X¹¹, and X¹² other than abridging group independently are a hydrogen atom or a substituted orunsubstituted alkyl or alkenyl group; each X⁸ is a substitutedcyclopentadienyl, indenyl, or fluorenyl group, any substituents on X⁸other than a bridging group and an alkenyl linking group independentlyare a hydrogen atom or a substituted or unsubstituted alkyl or alkenylgroup; each A¹ independently is a substituted or unsubstituted bridginggroup comprising either a cyclic group of 5 to 8 carbon atoms, abridging chain of 2 to 5 carbon atoms, or a carbon, silicon, germanium,tin, boron, nitrogen, or phosphorus bridging atom, any substituents onA¹ independently are a hydrogen atom, or a substituted or unsubstitutedaliphatic, aromatic, or cyclic group, or a combination thereof; each A²independently is a substituted bridging group comprising either asilicon bridging atom, a germanium bridging atom, a tin bridging atom, acarbon bridging atom, or a bridging chain of 2 to 5 carbon atoms, anysubstituents on A² other than the alkenyl linking group independentlyare a hydrogen atom, or a substituted or unsubstituted aliphatic,aromatic, or cyclic group, or a combination thereof; each M¹, M², and M³independently is Zr, Hf, or Ti; each E independently is carbon orsilicon; each R^(X), R^(Y), and R^(Z) independently is a hydrogen atom,or a substituted or unsubstituted aliphatic, aromatic, or cyclic group,or a combination thereof; and each n independently is an integer in arange from 0 to 12, inclusive.
 2. The compound of claim 1, wherein eachX¹, X², X⁵, X⁶, X⁹, and X¹⁰ independently is a methyl group, a phenylgroup, a benzyl group, or a halide.
 3. The compound of claim 1, whereineach substituent on X³, each substituent on X⁴ other than an alkenyllinking group, each substituent on X⁷, X¹¹, and X¹² other than abridging group, and each substituent on X⁸ other than a bridging groupand an alkenyl linking group, independently is a hydrogen atom, a methylgroup, an ethyl group, a propyl group, an n-butyl group, a t-butylgroup, or a hexyl group.
 4. The compound of claim 1, wherein: each X³independently is a substituted or unsubstituted cyclopentadienyl group;each X⁴ independently is a substituted cyclopentadienyl or substitutedindenyl group; X⁷ is a substituted fluorenyl group; X⁸ is a substitutedcyclopentadienyl group; and at least one of X¹¹ and X¹² is a substitutedfluorenyl group.
 5. The compound of claim 1, wherein each A¹ and A²independently comprises a carbon bridging atom or a bridging chain of 2to 5 carbon atoms.
 6. The compound of claim 1, wherein each substituenton A¹ and each substituent on A² other than an alkenyl linking groupindependently is a hydrogen atom, a methyl group, a phenyl group, acyclohexylphenyl group, or a naphthyl group.
 7. The compound of claim 1,wherein each M¹, M², and M³ independently is Zr or Hf, and each nindependently is 0, 1, 2, 3, 4, 5, or
 6. 8. The compound of claim 1,wherein the compound is:

wherein Ph is an abbreviation for phenyl.
 9. A catalyst compositioncomprising a contact product of the dinuclear metallocene compound ofclaim 1 and an aluminoxane compound, an organoboron or organoboratecompound, an ionizing ionic compound, or any combination thereof.
 10. Acatalyst composition comprising a contact product of the dinuclearmetallocene compound of claim 1 and an activator-support.
 11. Thecatalyst composition of claim 10, wherein the activator-supportcomprises a solid oxide treated with an electron-withdrawing anion. 12.The catalyst composition of claim 11, wherein: the solid oxide comprisessilica, alumina, silica-alumina, aluminum phosphate,heteropolytungstate, titania, zirconia, magnesia, boria, zinc oxide, amixed oxide thereof, or any mixture thereof; and theelectron-withdrawing anion comprises sulfate, bisulfate, fluoride,chloride, bromide, iodide, fluorosulfate, fluoroborate, phosphate,fluorophosphate, trifluoroacetate, triflate, fluorozirconate,fluorotitanate, or any combination thereof.
 13. The catalyst compositionof claim 10, wherein the activator-support comprises fluorided alumina,chlorided alumina, bromided alumina, sulfated alumina, fluoridedsilica-alumina, chlorided silica-alumina, bromided silica-alumina,sulfated silica-alumina, fluorided silica-zirconia, chloridedsilica-zirconia, bromided silica-zirconia, sulfated silica-zirconia,fluorided silica-titania, fluorided silica-clad alumina, or anycombination thereof.
 14. The catalyst composition of claim 10, furthercomprising an organoaluminum compound, wherein the organoaluminumcompound comprises trimethylaluminum, triethylaluminum,tri-n-propylaluminum, tri-n-butylaluminum, triisobutylaluminum,tri-n-hexylaluminum, tri-n-octylaluminum, diisobutylaluminum hydride,diethylaluminum ethoxide, diethylaluminum chloride, or any combinationthereof.
 15. A process for polymerizing olefins, the process comprisingcontacting the catalyst composition of claim 10 with an olefin monomerand optionally an olefin comonomer under polymerization conditions toproduce an olefin polymer.
 16. The process of claim 15, wherein theolefin monomer comprises ethylene and the olefin comonomer comprisespropylene, 1-butene, 2-butene, 3-methyl-1-butene, isobutylene,1-pentene, 2-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1-hexene,2-hexene, 3-ethyl-1-hexene, 1-heptene, 2-heptene, 3-heptene, 1-octene,1-decene, styrene, or mixtures thereof
 17. An olefin polymer produced bythe process of claim
 15. 18. A dinuclear metallocene compound having theformula:(IA)=(IB);(IIA)=(IIB); or(IIIA)=(IIIB); wherein:

wherein: X¹, X², X⁵, X⁶, X⁹, X¹⁰, X¹³, X¹⁴, X¹⁷, X¹⁸, X²¹, and X²²independently are hydrogen; BH₄; a halide; a hydrocarbyl group,hydrocarbyloxide group, hydrocarbyloxylate group, hydrocarbylaminogroup, or hydrocarbylsilyl group, any of which having up to 20 carbonatoms; or OBR^(A) ₂ or SO₃R^(A), wherein R^(A) is an alkyl group or arylgroup having up to 12 carbon atoms; X³ and X¹⁵ independently are asubstituted or unsubstituted cyclopentadienyl, indenyl, or fluorenylgroup, any substituents X³ and X¹⁵ independently are a hydrogen atom ora substituted or unsubstituted alkyl or alkenyl group; X⁴ and X¹⁶independently are a substituted cyclopentadienyl, indenyl, or fluorenylgroup, any substituents on X⁴ and X¹⁶ other than an alkenyl linkinggroup independently are a hydrogen atom or a substituted orunsubstituted alkyl or alkenyl group; X⁷, X¹¹, X¹², X¹⁹, X²³, and X²⁴independently are a substituted cyclopentadienyl, indenyl, or fluorenylgroup, any substituents on X⁷, X¹¹, X¹², X¹⁹, X²³, and X²⁴ other than abridging group independently are a hydrogen atom or a substituted orunsubstituted alkyl or alkenyl group; X⁸ and X²⁶ independently are asubstituted cyclopentadienyl, indenyl, or fluorenyl group, anysubstituents on X⁸ and X²⁰ other than a bridging group and an alkenyllinking group independently are a hydrogen atom or a substituted orunsubstituted alkyl or alkenyl group; A¹ and A³ independently are asubstituted or unsubstituted bridging group comprising either a cyclicgroup of 5 to 8 carbon atoms, a bridging chain of 2 to 5 carbon atoms,or a carbon, silicon, germanium, tin, boron, nitrogen, or phosphorusbridging atom, any substituents on A¹ and A³ independently are ahydrogen atom, or a substituted or unsubstituted aliphatic, aromatic, orcyclic group, or a combination thereof; A² and A⁴ independently are asubstituted bridging group comprising either a silicon bridging atom, agermanium bridging atom, a tin bridging atom, a carbon bridging atom, ora bridging chain of 2 to 5 carbon atoms, any substituents on A² and A⁴other than an alkenyl linking group independently are a hydrogen atom,or a substituted or unsubstituted aliphatic, aromatic, or cyclic group,or a combination thereof; M¹, M², M³, M⁴, M⁵, and M⁶ independently areZr, Hf, or Ti; each E independently is carbon or silicon; each R^(X),R^(Y), and R^(Z) independently is a hydrogen atom, or a substituted orunsubstituted aliphatic, aromatic, or cyclic group, or a combinationthereof; and each n independently is an integer in a range from 0 to 12,inclusive; with the proviso that (IA) is not the same as (IB), (IIA) isnot the same as (IIB), and (IIIA) is not the same as (IIIB).
 19. Acatalyst composition comprising a contact product of the dinuclearmetallocene compound of claim 18 and an aluminoxane compound, anorganoboron or organoborate compound, an ionizing ionic compound, or anycombination thereof
 20. A catalyst composition comprising a contactproduct of the dinuclear metallocene compound of claim 18 and anactivator-support.